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Question: Can individual molecules of indeno[1,2-a]fluorene switch between open-shell and closed-shell states?

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Context 1: Paper Info

Title: Bistability between π-diradical open-shell and closed-shell states in indeno[1,2-a]fluorene
Publish Date: Unkown
Author List: Shantanu Mishra (from IBM Research Europe -Zurich), Manuel Vilas-Varela (from Department of Organic Chemistry, Center for Research in Biological Chemistry and Molecular Materials (CiQUS), University of Santiago de Compostela), Leonard-Alexander Lieske (from IBM Research Europe -Zurich), Ricardo Ortiz (from Donostia International Physics Center (DIPC)), Igor Rončević (from Department of Chemistry, University of Oxford), Florian Albrecht (from IBM Research Europe -Zurich), Diego Peña (from Department of Organic Chemistry, Center for Research in Biological Chemistry and Molecular Materials (CiQUS), University of Santiago de Compostela), Leo Gross (from IBM Research Europe -Zurich)

Figure

Fig  1 | Non-benzenoid non-alternant polycyclic conjugated hydrocarbons a, Classical nonbenzenoid non-alternant polycyclic conjugated hydrocarbons: pentalene, azulene and heptalene b, Generation of indacenes and indenoindenes through benzinterposition and benzannelation of pentalene, respectively Gray filled rings represent Clar sextets c, Closed-shell Kekulé (left) and openshell non-Kekulé (right) resonance structures of QDMs Note that meta-QDM is a non-Kekulé molecule All indenofluorene isomers, being derived through benzannelation of indacenes, contain a central QDM moiety d, Closed-shell Kekulé (top) and open-shell non-Kekulé (bottom) resonance structures of indenofluorenes Compared to their closed-shell structures, 1 and 5 gain two Clar sextets in the openshell structure, while 2-4 gain only one Clar sextet in the open-shell structure Colored bonds in d highlight the ortho-and para-QDM moieties in the two closed-shell Kekulé structures of 5  e, Scheme of on-surface generation of 5 by voltage pulse-induced dehydrogenation of 6 (C20H14) Structures 7 and 8 represent the two monoradical species (C20H13) 
Fig  2 | Characterization of open-shell indeno[1,2-a]fluorene on bilayer NaCl/Au(111) a, DFTcalculated wave functions of the frontier orbitals of 5OS in the triplet configuration for the spin up (occupied) level (isovalue: 0 002 e -Å -3 ) Blue and red colors represent opposite phases of the wave function b, Corresponding DFT-calculated spin density of 5OS (isovalue: 0 01 e -Å -3) Blue and orange colors represent spin up and spin down densities, respectively c, Probability density of the SOMOs of 5OS (isovalue: 0 001 e -Å -3 ) d, DFT-calculated bond lengths of 5OS e, Constant-height I(V) spectra acquired on a species of 5 assigned as 5OS, along with the corresponding dI/dV(V) spectra Open feedback parameters: V = -2 V, I = 0 17 pA (negative bias side) and V = 2 V, I = 0 17 pA (positive bias side) Acquisition position of the spectra is shown in Supplementary Fig 7 f, Scheme of many-body transitions associated to the measured ionic resonances of 5OS Also shown are STM images of assigned 5OS at biases where the corresponding transitions become accessible Scanning parameters: I = 0 3 pA (V = -1 2V and -1 5 V) and 0 2 pA (V = 1 3 V and 1 6 V)  g, Laplace-filtered AFM image of assigned 5OS STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3Å The tip-height offset Δz for each panel is provided with respect to the STM setpoint, and positive (negative) values of Δz denote tip approach (retraction) from the STM setpoint f and g show the same molecule at the same adsorption site, which is next to a trilayer NaCl island The bright and dark features in the trilayer NaCl island in g correspond to Cl -and Na + ions, respectively Scale bars: 10 Å (f) and 5 Å (g) 
Fig  3 | Characterization of closed-shell indeno[1,2-a]fluorene on bilayer NaCl/Au(111) a, DFTcalculated wave functions of the frontier orbitals of closed-shell 5 0 (isovalue: 0 002 e -Å -3 ) The wave functions shown here are calculated for the 5para geometry b, DFT-calculated bond lengths of 5ortho (top) and 5para (bottom) c, Constant-height I(V) spectra acquired on a species of 5 assigned as 5para, along with the corresponding dI/dV(V) spectra Open feedback parameters: V = -2 V, I = 0 15 pA (negative bias side) and V = 2 2 V, I = 0 15 pA (positive bias side) Acquisition position of the spectra is shown in Supplementary Fig  7  d, Scheme of many-body transitions associated to the measured ionic resonances of 5para Also shown are STM images of assigned 5para at biases where the corresponding transitions become accessible Scanning parameters: I = 0 15 pA (V = -1 5 V) and 0 2 pA (V = 1 7 V)  e, Laplace-filtered AFM image of assigned 5para STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 7 Å  f, Selected bonds labeled for highlighting bond order differences between 5para and 5ortho For the bond pairs a/b, c/d and e/f, the bonds labeled in bold exhibit a higher bond order than their neighboring labeled bonds in 5para g, Laplace-filtered AFM images of 5 on bilayer NaCl/Cu(111) showing switching between 5OS and 5para as the molecule changes its adsorption position The faint protrusion adjacent to 5 is a defect that stabilizes the adsorption of 5  STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3Å  STM and STS data in c and d are acquired on the same species, while the AFM data in e is acquired on a different species Scale bars: 10 Å (d) and 5 Å (e,g) 
NMR (300 MHz, CDCl3) δ: 7 51 (m, 2H), 7 40 -7 28 (m, 5H), 7 27 -7 20 (m, 2H), 7 13 (d, J = 7 7 Hz, 1H), 2 07 (s, 3H), 1 77 (s, 3H) ppm  13C NMR-DEPT (75 MHz, CDCl3, 1:1 mixture of atropisomers) δ: 141 2 (C), 141 1 (C), 140 0 (C), 139 4 (2C), 137 5 (C), 137 4 (C), 136 0 (3C), 134 8 (C), 134 5 (C), 134 1 (C), 134 0 (C), 133 7 (C), 133 6 (C), 131 6 (CH), 131 2 (CH), 131 1 (CH), 130 7 (CH), 129 8 (CH), 129 7 (CH), 129 5 (CH), 129 4 (CH), 129 0 (CH), 128 9 (CH), 128 7 (2CH), 128 6 (2CH), 127 2 (CH), 127 1 (CH), 127 0 (CH), 126 9 (CH), 126 7 (CH), 126 6 (CH), 20 6 (CH3), 20 5 (CH3), 17 7 (CH3), 17 5 (CH3) ppm MS (APCI) m/z (%): 327 (M+1, 100) HRMS: C20H16Cl2; calculated: 327 0702, found: 327 0709 
NMR (500 MHz, CDCl3) δ: 7 93 (d, J = 7 6 Hz, 1H), 7 85 (d, J = 7 5 Hz, 1H), 7 78 (d, J = 7 7 Hz, 1H), 7 65 (d, J = 7 4 Hz, 1H), 7 61 (d, J = 7 5 Hz, 1H), 7 59 (d, J = 7 7 Hz, 1H), 7 47 (ddd, J = 8 4, 7 2, 1 1 Hz, 1H), 7 42 (dd, J = 8 1, 7 0 Hz, 1H), 7 35 (m, 2H), 4 22 (s, 3H), 4 02 (s, 3H) ppm  13C NMR-DEPT (125 MHz, CDCl3) δ: 144 1 (C), 143 3 (C), 142 3 (C), 141 9 (C), 141 8 (C), 141 2 (C), 138 2 (C), 136 5 (C), 127 0 (CH), 126 9 (CH), 126 7 (CH), 126 6 (CH), 125 3 (CH), 125 2 (CH), 123 6 (CH), 122 2 (CH), 119 9 (CH), 118 4 (CH), 37 4 (CH2), 36 3 (CH2) ppm MS (APCI) m/z (%): 254 (M+, 88) HRMS: C20H14; calculated: 254 1090, found: 254 1090 

abstract

Indenofluorenes are non-benzenoid conjugated hydrocarbons that have received great interest owing to their unusual electronic structure and potential applications in nonlinear optics and photovoltaics  Here, we report the generation of unsubstituted indeno[1,2-a]fluorene, the final and yet unreported parent indenofluorene regioisomer, on various surfaces by cleavage of two C-H bonds in 7,12-dihydro indeno[1,2-a]fluorene through voltage pulses applied by the tip of a combined scanning tunneling microscope and atomic force microscope 
On bilayer NaCl on Au(111), indeno[1,2a]fluorene is in the neutral charge state, while it exhibits charge bistability between neutral and anionic states on the lower work function surfaces of bilayer NaCl on Ag(111) and Cu(111)  In the neutral state, indeno[1,2-a]fluorene exhibits either of two ground states: an open-shell π-diradical state, predicted to be a triplet by density functional and multireference many-body perturbation theory calculations, or a closedshell state with a para-quinodimethane moiety in the as-indacene core 
Switching between open-and closed-shell states of a single molecule is observed by changing its adsorption site on NaCl  The inclusion of non-benzenoid carbocyclic rings is a viable route to tune the physicochemical properties of polycyclic conjugated hydrocarbons (PCHs)   Non-benzenoid polycycles may lead to local changes in strain, conjugation, aromaticity, and, relevant to the context of the present work, induce an open-shell ground state of the corresponding PCHs  
Many nonbenzenoid PCHs are also non-alternant, where the presence of odd-membered polycycles breaks the bipartite symmetry of the molecular network   Figure shows classical examples of non-benzenoid non-alternant PCHs, namely, pentalene, azulene and heptalene  Whereas azulene is a stable PCH exhibiting Hückel aromaticity ([4n+2] π-electrons, n = 2), pentalene and heptalene are unstable Hückel antiaromatic compounds with [4n] π-electrons, n = 2 (pentalene) and n = 3 (heptalene) 
Benzinterposition of pentalene generates indacenes, consisting of two isomers s-indacene and as-indacene (Fig  )  Apart from being antiaromatic, indacenes also contain proaromatic quinodimethane (QDM) moieties (Fig  ) , which endows them with potential open-shell character  While the parent s-indacene and asindacene have never been isolated, stable derivatives of s-indacene bearing bulky substituents have been synthesized  
A feasible strategy to isolate congeners of otherwise unstable non-benzenoid non-alternant PCHs is through fusion of benzenoid rings at the ends of the π-system, that is, benzannelation  For example, while the parent pentalene is unstable, the benzannelated congener indeno[2,1-a]indene is stable under ambient conditions (Fig  )  
However, the position of benzannelation is crucial for stability: although indeno[2,1a]indene is stable, its regioisomer indeno[1,2-a]indene (Fig  ) oxidizes under ambient conditions   Similarly, benzannelation of indacenes gives rise to the family of PCHs known as indenofluorenes (Fig  ), which constitute the topic of the present work 
Depending on the benzannelation position and the indacene core, five regioisomers can be constructed, namely, indeno [ Practical interest in indenofluorenes stems from their low frontier orbital gap and excellent electrochemical characteristics that render them as useful components in organic electronic devices  
The potential open-shell character of indenofluorenes has led to several theoretical studies on their use as non-linear optical materials and as candidates for singlet fission in organic photovoltaics   Recent theoretical work has also shown that indenofluorene-based ladder polymers may exhibit fractionalized excitations 
Fundamentally, indenofluorenes represent model systems to study the interplay between aromaticity and magnetism at the molecular scale   Motivated by many of these prospects, the last decade has witnessed intensive synthetic efforts toward the realization of indenofluorenes  Derivatives of 1-4 have been realized in solution , while 1-3 have also been synthesized on surfaces and characterized using scanning tunneling microscopy (STM) and atomic force microscopy (AFM), which provide information on molecular orbital densities , molecular structure and oxidation state  
With regards to the open-shell character of indenofluorenes, 2-4 are theoretically and experimentally interpreted to be closed-shell, while calculations indicate that 1 and 5 should exhibit open-shell ground states   Bulk characterization of mesitylsubstituted 1, including X-ray crystallography, temperature-dependent NMR, and electron spin resonance spectroscopy, provided indications of its open-shell ground state  
Electronic characterization of 1 on Au(111) surface using scanning tunneling spectroscopy (STS) revealed a low electronic gap of 0 4 eV (ref  )  However, no experimental proof of an openshell ground state of 1 on Au(111), such as detection of singly occupied molecular orbitals (SOMOs) or spin excitations and correlations due to unpaired electrons , was shown 
In this work, we report the generation and characterization of unsubstituted 5  Our research is motivated by theoretical calculations that indicate 5 to exhibit the largest diradical character among all indenofluorene isomers   The same calculations also predict that 5 should possess a triplet ground state 
Therefore, 5 would qualify as a Kekulé triplet, of which only a handful of examples exist   However, definitive synthesis of 5 has never been reported so far  Previously, Dressler et al  reported transient isolation of mesityl-substituted 5, where it decomposed both in the solution and in solid state , and only the structural proof of the corresponding dianion was obtained 
On-surface generation of a derivative of 5, starting from truxene as a precursor, was recently reported   STM data on this compound, containing the indeno[1,2-a]fluorene moiety as part of a larger PCH, was interpreted to indicate its open-shell ground state  However, the results did not imply the ground state of unsubstituted 5  Here, we show that on insulating surfaces 5 can exhibit either of two ground states: an open-shell or a closed-shell 
We infer the existence of these two ground states based on high-resolution AFM imaging with bond-order discrimination and STM imaging of molecular orbital densities   AFM imaging reveals molecules with two different geometries  Characteristic bond-order differences in the two geometries concur with the geometry of either an open-or a closed-shell state 
Concurrently, STM images at ionic resonances show molecular orbital densities corresponding to SOMOs for the open-shell geometry, but orbital densities of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for the closed-shell geometry  Our experimental results are in good agreement with density functional theory (DFT) and multireference perturbation theory calculations 
Finally, we observe switching between open-and closed-shell states of a single molecule by changing its adsorption site on the surface  Synthetic strategy toward indeno[1,2-a]fluorene  The generation of 5 relies on the solution-phase synthesis of the precursor 7,12-dihydro indeno[1,2-a]fluorene (6)  Details on synthesis and characterization of 6 are reported in Supplementary Figs 
  Single molecules of 6 are deposited on coinage metal (Au(111), Ag(111) and Cu(111)) or insulator surfaces  In our work, insulating surfaces correspond to two monolayer-thick (denoted as bilayer) NaCl on coinage metal surfaces  Voltage pulses ranging between 4-6 V are applied by the tip of a combined STM/AFM system, which result in cleavage of one C-H bond at each of the pentagonal apices of 6, thereby leading to the generation of 5 (Fig  ) 
In the main text, we focus on the generation and characterization of 5 on insulating surfaces  Generation and characterization of 5 on coinage metal surfaces is shown in Supplementary Fig    )  Blue and orange colors represent spin up and spin down densities, respectively  c, Probability density of the SOMOs of 5OS (isovalue: 0 001 e -Å -3 ) 
d, DFT-calculated bond lengths of 5OS  e, Constant-height I(V) spectra acquired on a species of 5 assigned as 5OS, along with the corresponding dI/dV(V) spectra  Open feedback parameters: V = -2 V, I = 0 17 pA (negative bias side) and V = 2 V, I = 0 17 pA (positive bias side)  Acquisition position of the spectra is shown in Supplementary Fig    f, Scheme of many-body transitions associated to the measured ionic resonances of 5OS 
Also shown are STM images of assigned 5OS at biases where the corresponding transitions become accessible  Scanning parameters: I = 0 3 pA (V = -1 2 V and -1 5 V) and 0 2 pA (V = 1 3 V and 1 6 V)  g, Laplace-filtered AFM image of assigned 5OS  STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3
Å  The tip-height offset Δz for each panel is provided with respect to the STM setpoint, and positive (negative) values of Δz denote tip approach (retraction) from the STM setpoint  f and g show the same molecule at the same adsorption site, which is next to a trilayer NaCl island  The bright and dark features in the trilayer NaCl island in g correspond to Cl -and Na + ions, respectively 
Scale bars: 10 Å (f) and 5 Å (g)  To experimentally explore the electronic structure of 5, we used bilayer NaCl films on coinage metal surfaces to electronically decouple the molecule from the metal surfaces  Before presenting the experimental findings, we summarize the results of our theoretical calculations performed on 5 in the neutral charge state (denoted as 5 0 ) 
We start by performing DFT calculations on 5 0 in the gas phase  Geometry optimization performed at the spin-unrestricted UB3LYP/6-31G level of theory leads to one local minimum, 5OS, the geometry of which corresponds to the open-shell resonance structure of 5 (Fig  , the label OS denotes open-shell) 
The triplet electronic configuration of 5OS is the lowest-energy state, with the openshell singlet configuration 90 meV higher in energy  Geometry optimization performed at the restricted closed-shell RB3LYP/6-31G level reveals two local minima, 5para and 5ortho, the geometries of which (Fig  ) exhibit bond length alternations in line with the presence of a para-or an ortho-QDM moiety, respectively, in the as-indacene core of the closed-shell resonance structures of 5 (Fig  )  
Relative to 5OS in the triplet configuration, 5para and 5ortho are 0 40 and 0 43 eV higher in energy, respectively  Additional DFT results are shown in Supplementary Fig    To gain more accurate insights into the theoretical electronic structure of 5, we performed multireference perturbation theory calculations (Supplementary Fig  ) based on quasi-degenerate second-order n-electron valence state perturbation theory (QD-NEVPT2) 
In so far as the order of the ground and excited states are concerned, the results of QD-NEVPT2 calculations qualitatively match with DFT calculations  For 5OS, the triplet configuration remains the lowest-energy state, with the open-shell singlet configuration 60 meV higher in energy  The energy differences between the open-and closed-shell states are substantially reduced in QD-NEVPT2 calculations, with 5para and 5ortho only 0 11 and 0 21 eV higher in energy, respectively, compared to 5OS in the triplet configuration 
We also performed nucleus-independent chemical shift calculations to probe local aromaticity of 5 in the openand closed-shell states  While 5OS in the triplet configuration exhibits local aromaticity at the terminal benzenoid rings, 5OS in the open-shell singlet configuration, 5para and 5ortho all display antiaromaticity (Supplementary Fig  ) 
The choice of the insulating surface determines the charge state of 5: while 5 adopts neutral charge state on the high work function bilayer NaCl/Au(111) surface (irrespective of its openor closed-shell state, Supplementary Fig  ), 5 exhibits charge bistability between 5 0 and the anionic state 5 -1 on the lower work function bilayer NaCl/Ag(111) and Cu(111) surfaces (Supplementary Figs  ) 
In the main text, we focus on the characterization of 5 on bilayer NaCl/Au(111)  Characterization of charge bistable 5 is reported in Supplementary Figs    We first describe experiments on 5 on bilayer NaCl/Au(111), where 5 exhibits a geometry corresponding to the calculated 5OS geometry, and an open-shell electronic configuration 
We compare the experimental data on this species to calculations on 5OS with a triplet configuration, as theory predicts a triplet ground state for 5OS  For 5OS, the calculated frontier orbitals correspond to the SOMOs ψ1 and ψ2 (Fig  ), whose spin up levels are occupied and the spin down levels are empty 
Figure shows the DFT-calculated bond lengths of 5OS, where the two salient features, namely, the small difference in the bond lengths within each ring and the notably longer bond lengths in the pentagonal rings, agree with the open-shell resonance structure of 5 (Fig  )  Figure shows an AFM image of 5 adsorbed on bilayer NaCl/Au(111) that we assign as 5OS, where the bond-order differences qualitatively correspond to the calculated 5OS geometry (discussed and compared to the closed-shell state below) 
Differential conductance spectra (dI/dV(V), where I and V denote the tunneling current and bias voltage, respectively) acquired on assigned 5OS exhibit two peaks centered at -1 5 V and 1 6 V (Fig  ), which we assign to the positive and negative ion resonances (PIR and NIR), respectively  Figure shows the corresponding STM images acquired at the onset (V = -1 2
V/1 3 V) and the peak (V = -1 5 V/1 6 V) of the ionic resonances  To draw a correspondence between the STM images and the molecular orbital densities, we consider tunneling events as many-body electronic transitions between different charge states of 5OS (Fig  )  Within this framework, the PIR corresponds to transitions between 5 0 and the cationic state 5  
At the onset of the PIR at -1 2 V, an electron can only be detached from the SOMO ψ1 and the corresponding STM image at -1 2 V shows the orbital density of ψ1  Increasing the bias to the peak of the PIR at -1 5 V, it becomes possible to also empty the SOMO ψ2, such that the corresponding STM image shows the superposition of ψ1 and ψ2, that is, |ψ1| 2 + |ψ2| 2 (ref 
)  Similarly, the NIR corresponds to transitions between 5 0 and 5 -1   At the NIR onset of 1 3 V, only electron attachment to ψ2 is energetically possible  At 1 6 V, electron attachment to ψ1 also becomes possible, and the corresponding STM image shows the superposition of ψ1 and ψ2  The observation of the orbital densities of SOMOs, and not the hybridized HOMO and LUMO, proves the open-shell ground state of assigned 5OS 
Measurements of the monoradical species with a doublet ground state are shown in Supplementary Fig    Unexpectedly, another species of 5 was also experimentally observed that exhibited a closedshell ground state  In contrast to 5OS, where the frontier orbitals correspond to the SOMOs ψ1 and ψ2, DFT calculations predict orbitals of different shapes and symmetries for 5para and 5ortho, denoted as α and β and shown in Fig   
For 5ortho, α and β correspond to HOMO and LUMO, respectively  The orbitals are inverted in energy and occupation for 5para, where β is the HOMO and α is the LUMO  Fig  shows an AFM image of 5 that we assign as 5para  We experimentally infer its closed-shell state first by using qualitative bond order discrimination by AFM 
In high-resolution AFM imaging, chemical bonds with higher bond order are imaged brighter (that is, with higher frequency shift Δf) due to stronger repulsive forces, and they appear shorter   In Fig  , we label seven bonds whose bond orders show significant qualitative differences in the calculated 5ortho, 5para (Fig  ) and 5OS (Fig  ) geometries 
In 5para, the bonds b and d exhibit a higher bond order than a and c, respectively  This pattern is reversed for 5ortho, while the bond orders of the bonds a-d are all similar and small for 5OS  Furthermore, in 5para bond f exhibits a higher bond order than e, while in 5ortho and 5OS bonds e and f exhibit similar bond order (because they belong to Clar sextets) 
Finally, the bond labeled g shows a higher bond order in 5para than in 5ortho and 5OS  The AFM image of assigned 5para shown in Fig  indicates higher bond orders of the bonds b, d and f compared to a, c and e, respectively  In addition, the bond g appears almost point-like and with enhanced Δf contrast compared to its neighboring bonds, indicative of a high bond order (see Supplementary Fig  for height-dependent measurements) 
These observations concur with the calculated 5para geometry (Fig  )  Importantly, all these distinguishing bond-order differences are distinctly different in the AFM image of 5OS shown in Fig  , which is consistent with the calculated 5OS geometry (Fig  )  In the AFM images of 5OS (Fig  and Supplementary Fig  ), the bonds a-d at the pentagon apices appear with similar contrast and apparent bond length 
The bonds e and f at one of the terminal benzenoid rings also exhibit similar contrast and apparent bond length, while the central bond g appears longer compared to assigned 5para  Further compelling evidence for the closed-shell state of assigned 5para is obtained by STM and STS  dI/dV(V) spectra acquired on an assigned 5para species exhibit two peaks centered at -1 4 V (PIR) and 1 6 V (NIR) (Fig  ) 
STM images acquired at these biases (Fig  ) show the orbital densities of β (-1 4 V) and α (1 6 V)  First, the observation of α and β as the frontier orbitals of this species, and not the SOMOs, strongly indicates its closed-shell state  Second, consistent with AFM measurements that indicate good correspondence to the calculated 5para geometry, we observe β as the HOMO and α as the LUMO 
For 5ortho, α should be observed as the HOMO and β as the LUMO  We did not observe molecules with the signatures of 5ortho in our experiments  We observed molecules in open-(5OS, Fig  ) and closed-shell (5para, Fig  ) states in similar occurrence after their generation from 6 on the surface  We could also switch individual molecules between open-and closed-shell states as shown in Fig  and Supplementary Fig   
To this end, a change in the adsorption site of a molecule was induced by STM imaging at ionic resonances, which often resulted in movement of the molecule  The example presented in Fig  shows a molecule that was switched from 5para to 5OS and back to 5para  The switching is not directed, that is, we cannot choose which of the two species will be formed when changing the adsorption site, and we observed 5OS and 5para in approximately equal yields upon changing the adsorption site 
The molecule in Fig  is adsorbed on top of a defect that stabilizes its adsorption geometry on bilayer NaCl  At defect-free adsorption sites on bilayer NaCl, that is, without a third layer NaCl island or atomic defects in the vicinity of the molecule, 5 could be stably imaged neither by AFM nor by STM at ionic resonances (Supplementary Fig  ) 
Without changing the adsorption site, the state of 5 (open-or closedshell) never changed, including the experiments on bilayer NaCl/Ag(111) and Cu(111), on which the charge state of 5 could be switched (Supplementary Figs  )  Also on these lower work function surfaces, both open-and closed-shell species were observed for 5 0 and both showed charge bistability between 5 0 (5OS or 5para) and 5 -1 (Supplementary Figs  ) 
The geometrical structure of 5 -1 probed by AFM, and its electronic structure probed by STM imaging at the NIR (corresponding to transitions between 5 -1 and the dianionic state 5 -2 ), are identical within the measurement accuracy for the charged species of both 5OS and 5para  When cycling the charge state of 5 between 5 0 and 5 -1 several times, we always observed the same state (5OS or 5para) when returning to 5 0 , provided the molecule did not move during the charging/discharging process 
Based on our experimental observations we conclude that indeno[1,2-a]fluorene (5), the last unknown indenofluorene isomer, can be stabilized in and switched between an open-shell (5OS) and a closed-shell (5para) state on NaCl  For the former, both DFT and QD-NEVPT2 calculations predict a triplet electronic configuration 
Therefore, 5 can be considered to exhibit the spin-crossover effect, involving magnetic switching between high-spin (5OS) and low-spin (5para) states, coupled with a reversible structural transformation  So far, the spin-crossover effect has mainly only been observed in transition-metal-based coordination compounds with a near-octahedral geometry  
The observation that the switching between open-and closedshell states is related to changes in the adsorption site but is not achieved by charge-state cycling alone, indicates that the NaCl surface and local defects facilitate different electronic configurations of 5 depending on the adsorption site 
Gas-phase QD-NEVPT2 calculations predict that 5OS is the ground state, and the closed-shell 5para and 5ortho states are 0 11 and 0 21 eV higher in energy  The experiments, showing bidirectional switching between 5OS and 5para, indicate that a change in the adsorption site can induce sufficient change in the geometry of 5 (leading to a corresponding change in the ground state electronic configuration) and thus induce switching 
Switching between open-and closed-shell states in 5 does not require the breaking or formation of covalent bonds , but a change of adsorption site on NaCl where the molecule is physisorbed  Our results should have implications for single-molecule devices, capitalizing on the altered electronic and chemical properties of a system in π-diradical open-shell and closed-shell states such as frontier orbital and singlet-triplet gaps, and chemical reactivity 
For possible future applications as a single-molecule switch, it might be possible to also switch between open-and closed-shell states by changing the local electric field, such as by using chargeable adsorbates   Scanning probe microscopy measurements and sample preparation  STM and AFM measurements were performed in a home-built system operating at base pressures below 1×10 -10 mbar and a base temperature of 5 K  Bias voltages are provided with respect to the sample 
All STM, AFM and spectroscopy measurements were performed with carbon monoxide (CO) functionalized tips  AFM measurements were performed in non-contact mode with a qPlus sensor   The sensor was operated in frequency modulation mode with a constant oscillation amplitude of 0 5 Å  STM measurements were performed in constantcurrent mode, AFM measurements were performed in constant-height mode with V = 0 V, and I(V) and Δf(V) spectra were acquired in constant-height mode 
Positive (negative) values of the tip-height offset Δz represent tip approach (retraction) from the STM setpoint  All dI/dV(V) spectra are obtained by numerical differentiation of the corresponding I(V) spectra  STM and AFM images, and spectroscopy curves, were post-processed using Gaussian low-pass filters 
Au(111), Ag(111) and Cu(111) surfaces were cleaned by iterative cycles of sputtering with Ne + ions and annealing up to 800 K  NaCl was thermally evaporated on Au(111), Ag(111) and Cu(111) surfaces held at 323 K, 303 K and 283 K, respectively  This protocol results in the growth of predominantly bilayer (100)-terminated islands, with a minority of trilayer islands 
Sub-monolayer coverage of 6 on surfaces was obtained by flashing an oxidized silicon wafer containing the precursor molecules in front of the cold sample in the microscope  CO molecules for tip functionalization were dosed from the gas phase on the cold sample  Density functional theory calculations  DFT was employed using the PSI4 program package  
All molecules with different charge (neutral and anionic) and electronic (open-and closed-shell) states were independently investigated in the gas phase  The B3LYP exchangecorrelation functional with 6-31G basis set was employed for structural relaxation and singlepoint energy calculations  The convergence criteria were set to 10 −4 eV Å −1 for the total forces and 10 −6 eV for the total energies 
Multireference calculations  Multireference calculations were performed on the DFToptimized geometries using the QD-NEVPT2 level of theory , with three singlet roots and one triplet root included in the state-averaged calculation  A (10,10) active space (that is, 10 electrons in 10 orbitals) was used along with the def2-TZVP basis set  
Increasing either the active space size or expanding the basis set resulted in changes of about 50 meV for relative energies of the singlet and triplet states  These calculations were performed using the ORCA program package   Nucleus-independent chemical shift (NICS) calculations  Isotropic nucleus-independent chemical shift values were evaluated at the centre of each ring using the B3LYP exchangecorrelation functional with def2-TZVP basis set using the Gaussian 16 software package  
Starting materials (reagent grade) were purchased from TCI and Sigma-Aldrich and used without further purification  Reactions were carried out in flame-dried glassware and under an inert atmosphere of purified Ar using Schlenk techniques  Thin-layer chromatography (TLC) was performed on Silica Gel 60 F-254 plates (Merck) 
Column chromatography was performed on silica gel (40-60 µm)  Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Varian Mercury 300 or Bruker Varian Inova 500 spectrometers  Mass spectrometry (MS) data were recorded in a Bruker Micro-TOF spectrometer  The synthesis of compound 6 was developed following the two-step synthetic route shown in Supplementary Fig  , which is based on the preparation of methylene-bridge polyarenes by means of Pd-catalyzed activation of benzylic C-H bonds  
Supplementary Figure | Synthetic route to obtain compound 6  The complex Pd2(dba)3 (20 mg, 0 02 mmol) was added over a deoxygenated mixture of 1,3-dibromo-2,4-dimethylbenzene (9, 100 mg, 0 38 mmol), boronic acid 10 (178 mg, 1 14 mmol), K2CO3 (314 mg, 2 28 mmol) and XPhos (35 mg, 0 08 mmol) in toluene (1:1, 10 mL), and the resulting mixture was heated at 90 °C for 2 h 
After cooling to room temperature, the solvents were evaporated under reduced pressure  The reaction crude was purified by column chromatography (SiO2; hexane:CH2Cl2 9:1) affording 11 (94 mg, 76%) as a colorless oil  The complex Pd(OAc)2 (7 mg, 0 03 mmol) was added over a deoxygenated mixture of terphenyl 11 (90 mg, 0 27 mmol), K2CO3 (114 mg, 0 83 mmol) and ligand L (26 mg, 0 06 mmol) in NMP (2 mL) 
The resulting mixture was heated at 160 °C for 4 h  After cooling to room temperature, H2O (30 mL) was added, and the mixture was extracted with EtOAc (3x15 mL)  The combined organic extracts were dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure  The reaction crude was purified by column chromatography (SiO2; hexane:CH2Cl2 9:1) affording compound 6 (8 mg, 11%) as a white solid  in AFM imaging due to their reduced adsorption height compared to the rest of the carbon atoms 
We attribute this observation to the significantly different lattice parameter of Cu(111) (2 57 Å) compared to Au(111) and Ag(111) (2 95 Å and 2 94 Å, respectively) , such that the apical carbon atoms of the pentagonal rings of 5 adsorb on the on-top atomic sites on Au(111) and Ag(111), but not on Cu(111) 
Our speculation is based on a previous study of polymers of 1 on Au(111) by Di Giovannantonio et al  , where both tilted and planar individual units of 1 were observed depending on whether the apical carbon atoms of the pentagonal rings in 1 adsorbed on the on-top or hollow sites of the surface, respectively 
Given the strong molecule-metal interaction, we found no electronic state signatures of 5 on all three metal surfaces  STM set point for AFM images: V = 0  e, Frontier orbital spectrum of 5 -1   In the anionic state, ψ2 becomes doubly occupied and ψ1 is the SOMO  Filled and empty circles denote occupied and empty orbitals, respectively 
For each panel, zero of the energy axis has been aligned to the respective highest-energy occupied orbital 
Context 2: \section{Introduction}

Spectral line surveys have revealed that high-mass star-forming
regions are rich reservoirs of molecules from simple diatomic species
to complex and larger molecules (e g ,
\citealt{schilke1997b,hatchell1998b,comito2005,bisschop2007}) 
However, there have been rarely studies undertaken to investigate the
chemical evolution during massive star formation from the earliest
evolutionary stages, i e , from High-Mass Starless Cores (HMSCs) and
High-Mass Cores with embedded low- to intermediate-mass protostars
destined to become massive stars, via High-Mass Protostellar Objects
(HMPOs) to the final stars that are able to produce Ultracompact H{\sc
  ii} regions (UCH{\sc ii}s, see \citealt{beuther2006b} for a recent
description of the evolutionary sequence)  The first two evolutionary
stages are found within so-called Infrared Dark Clouds (IRDCs)   While
for low-mass stars the chemical evolution from early molecular
freeze-out to more evolved protostellar cores is well studied (e g ,
\citealt{bergin1997,dutrey1997,pavlyuchenkov2006,joergensen2007}),
it is far from clear whether similar evolutionary patterns are present
during massive star formation 

To better understand the chemical evolution of high-mass star-forming
regions we initiated a program to investigate the chemical properties
from IRDCs to UCH{\sc ii}s from an observational and theoretical
perspective  We start with single-dish line surveys toward a large
sample obtaining their basic characteristics, and then perform
detailed studies of selected sources using interferometers on smaller
scales  These observations are accompanied by theoretical modeling of
the chemical processes   Long-term goals are the chemical
characterization of the evolutionary sequence in massive star
formation, the development of chemical clocks, and the identification
of molecules as astrophysical tools to study the physical processes
during different evolutionary stages  Here, we present an initial
study of the reactive radical ethynyl (C$_2$H) combining single-dish
and interferometer observations with chemical modeling   Although
C$_2$H was previously observed in low-mass cores and Photon Dominated
Regions (e g , \citealt{millar1984,jansen1995}), so far it was not
systematically investigated in the framework of high-mass star
formation 

\section{Observations}
\label{obs}

The 21 massive star-forming regions were observed with the Atacama
Pathfinder Experiment (APEX) in the 875\,$\mu$m window in fall 2006 
We observed 1\,GHz from 338 to 339\,GHz and 1\,GHz in the image
sideband from 349 to 350\,GHz   The spectral resolution was
0 1\,km\,s$^{-1}$, but we smoothed the data to
$\sim$0 9\,km\,s$^{-1}$  The average system temperatures were around
200\,K, each source had on-source integration times between 5 and 16
min  The data were converted to main-beam temperatures with forward
and beam efficiencies of 0 97 and 0 73, respectively
\citep{belloche2006}  The average $1\sigma$ rms was 0 4\,K   The main
spectral features of interest are the C$_2$H lines around 349 4\,GHz
with upper level excitation energies $E_u/k$ of 42\,K (line blends of
C$_2$H$(4_{5,5}-3_{4,4})$ \& C$_2$H$(4_{5,4}-3_{4,3})$ at
349 338\,GHz, and C$_2$H$(4_{4,4}-3_{3,3})$ \&
C$_2$H$(4_{4,3}-3_{3,2})$ at 349 399\,GHz)  The beam size was $\sim
18''$ 

The original Submillimeter Array (SMA) C$_2$H data toward the
HMPO\,18089-1732 were first presented in \citet{beuther2005c}  There
we used the compact and extended configurations resulting in good
images for all spectral lines except of C$_2$H  For this project, we
re-worked on these data only using the compact configuration  Because
the C$_2$H emission is distributed on larger scales (see
\S\ref{results}), we were now able to derive a C$_2$H image  The
integration range was from 32 to 35\,km\,s$^{-1}$, and the achieved
$1\sigma$ rms of the C$_2$H image was 450\,mJy\,beam$^{-1}$   For more
details on these observations see \citet{beuther2005c} 

\section{Results}
\label{results}

The sources were selected to cover all evolutionary stages from IRDCs
via HMPOs to UCH{\sc ii}s  We derived our target list from the samples
of \citet{klein2005,fontani2005,hill2005,beltran2006}   Table
\ref{sample} lists the observed sources, their coordinates, distances,
luminosities and a first order classification into the evolutionary
sub-groups IRDCs, HMPOs and UCH{\sc ii}s based on the previously
available data  Although this classification is only based on a
limited set of data, here we are just interested in general
evolutionary trends  Hence, the division into the three main classes
is sufficient 

Figure \ref{spectra} presents sample spectra toward one source of each
evolutionary group  While we see several CH$_3$OH lines as well as
SO$_2$ and H$_2$CS toward some of the HMPOs and UCH{\sc ii}s but not
toward the IRDCs, the surprising result of this comparison is the
presence of the C$_2$H lines around 349 4\,GHz toward all source types
from young IRDCs via the HMPOs to evolved UCH{\sc ii}s   Table
\ref{sample} lists the peak brightness temperatures, the integrated
intensities and the FWHM line-widths of the C$_2$H line blend at
349 399\,GHz  The separation of the two lines of 1 375\,MHz already
corresponds to a line-width of 1 2\,km\,s$^{-1}$  We have three C$_2$H
non-detections (2 IRDCs and 1 HMPO), however, with no clear trend with
respect to the distances or the luminosities (the latter comparison is
only possible for the HMPOs)  While IRDCs are on average colder than
more evolved sources, and have lower brightness temperatures, the
non-detections are more probable due to the relatively low sensitivity
of the short observations (\S\ref{obs})  Hence, the data indicate
that the C$_2$H lines are detected independent of the evolutionary
stage of the sources in contrast to the situation with other
molecules   When comparing the line-widths between the different
sub-groups, one finds only a marginal difference between the IRDCs and
the HMPOs (the average $\Delta v$ of the two groups are 2 8 and
3 1\,km\,s$^{-1}$)   However, the UCH{\sc ii}s exhibit significantly
broader line-widths with an average value of 5 5\,km\,s$^{-1}$ 

Intrigued by this finding, we wanted to understand the C$_2$H spatial
structure during the different evolutionary stages   Therefore, we
went back to a dataset obtained with the Submillimeter Array toward
the hypercompact H{\sc ii} region IRAS\,18089-1732 with a much higher
spatial resolution of $\sim 1''$ \citep{beuther2005c}   Albeit this
hypercompact H{\sc ii} region belongs to the class of HMPOs, it is
already in a relatively evolved stage and has formed a hot core with a
rich molecular spectrum   \citet{beuther2005c} showed the spectral
detection of the C$_2$H lines toward this source, but they did not
present any spatially resolved images  To recover large-scale
structure, we restricted the data to those from the compact SMA
configuration (\S\ref{obs})  With this refinement, we were able to
produce a spatially resolved C$_2$H map of the line blend at
349



ground_truth: Yes, individual molecules of indeno[1,2-a]fluorene can switch between open-shell and closed-shell states by changing their adsorption site on the surface.

prompt_front: Now, answer the following question based on the text below, only give me the answer and do not output any other words.

Question: What molecule was the focus of the study?

Read the following text and answer briefly.

Context 2: 338\,GHz with an angular resolution of $2 9''\times 1 4''$
(corresponding to an average linear resolution of 7700\,AU at the
given distance of 3 6\,kpc)  Figure \ref{18089} presents the
integrated C$_2$H emission with a contour overlay of the 860\,$\mu$m
continuum source outlining the position of the massive protostar  In
contrast to almost all other molecular lines that peak along with the
dust continuum \citep{beuther2005c}, the C$_2$H emission surrounds the
continuum peak in a shell-like fashion 

\section{Discussion and Conclusions}

To understand the observations, we conducted a simple chemical
modeling of massive star-forming regions  A 1D cloud model with a mass
of 1200\,M$_\sun$, an outer radius of 0 36\,pc and a power-law density
profile ($\rho\propto r^p$ with $p=-1 5$) is the initially assumed
configuration  Three cases are studied: (1) a cold isothermal cloud
with $T=10$\,K, (2) $T=50$\,K, and (3) a warm model with a temperature
profile $T\propto r^q$ with $q=-0 4$ and a temperature at the outer
radius of 44\,K  The cloud is illuminated by the interstellar UV
radiation field (IRSF, \citealt{draine1978}) and by cosmic ray
particles (CRP)  The ISRF attenuation by single-sized $0 1\mu$m
silicate grains at a given radius is calculated in a plane-parallel
geometry following \citet{vandishoeck1988}  The CRP ionization rate is
assumed to be $1 3\times 10^{-17}$~s$^{-1}$ \citep{spitzer1968}  The
gas-grain chemical model by \citet{vasyunin2008} with the desorption
energies and surface reactions from \citet{garrod2006} is used 
Gas-phase reaction rates are taken from RATE\,06 \citep{woodall2007},
initial abundances, were adopted from the ``low metal'' set of
\citet{lee1998} 

Figure \ref{model} presents the C$_2$H abundances for the three models
at two different time steps: (a) 100\,yr, and (b) in a more evolved
stage after $5\times10^4$\,yr  The C$_2$H abundance is high toward the
core center right from the beginning of the evolution, similar to
previous models (e g , \citealt{millar1985,herbst1986,turner1999}) 
During the evolution, the C$_2$H abundance stays approximately
constant at the outer core edges, whereas it decreases by more than
three orders of magnitude in the center, except for the cold $T=10$~K
model   The C$_2$H abundance profiles for all three models show
similar behavior 

The chemical evolution of ethynyl is determined by relative removal
rates of carbon and oxygen atoms or ions into molecules like CO, OH,
H$_2$O  Light ionized hydrocarbons CH$^+_{\rm n}$ (n=2  5) are quickly
formed by radiative association of C$^+$ with H$_2$ and hydrogen
addition reactions: C$^+$ $\rightarrow$ CH$_2^+$ $\rightarrow$
CH$_3^+$ $\rightarrow$ CH$_5^+$   The protonated methane reacts with
electrons, CO, C, OH, and more complex species at later stage and
forms methane   The CH$_4$ molecules undergo reactive collisions with
C$^+$, producing C$_2$H$_2^+$ and C$_2$H$_3^+$  An alternative way to
produce C$_2$H$_2^+$ is the dissociative recombination of CH$_5^+$
into CH$_3$ followed by reactions with C$^+$   Finally, C$_2$H$_2^+$
and C$_2$H$_3^+$ dissociatively recombine into CH, C$_2$H, and
C$_2$H$_2$  The major removal for C$_2$H is either the direct
neutral-neutral reaction with O that forms CO, or the same reaction
but with heavier carbon chain ions that are formed from C$_2$H by
subsequent insertion of carbon  At later times, depletion and
gas-phase reactions with more complex species may enter into this
cycle   At the cloud edge the interstellar UV radiation
instantaneously dissociates CO despite its self-shielding,
re-enriching the gas with elemental carbon 

The transformation of C$_2$H into CO and other species proceeds
efficiently in dense regions, in particular in the ``warm'' model
where endothermic reactions result in rich molecular complexity of the
gas (see Fig ~\ref{model})   In contrast, in the ``cold'' 10\,K model
gas-grain interactions and surface reactions become important   As a
result, a large fraction of oxygen is locked in water ice that is hard
to desorb ($E_{\rm des} \sim 5500$~K), while half of the elemental
carbon goes to volatile methane ice ($E_{\rm des} \sim 1300$~K)  Upon
CRP heating of dust grains, this leads to much higher gas-phase
abundance of C$_2$H in the cloud core for the cold model compared to
the warm model  The effect is not that strong for less dense regions
at larger radii from the center 

Since the C$_2$H emission is anti-correlated with the dust continuum
emission in the case of IRAS\,18089-1732 (Fig \,\ref{18089}), we do
not have the H$_2$ column densities to quantitatively compare the
abundance profiles of IRAS\,18089-1732 with our model  However, data
and model allow a qualitative comparison of the spatial structures 
Estimating an exact evolutionary time for IRAS\,18089-1732 is hardly
possible, but based on the strong molecular line emission, its high
central gas temperatures and the observed outflow-disk system
\citep{beuther2004a,beuther2004b,beuther2005c}, an approximate age of
$5\times10^4$\,yr appears reasonable   Although dynamical and chemical
times are not necessarily exactly the same, in high-mass star
formation they should not differ to much: Following the models by
\citet{mckee2003} or \citet{krumholz2006b}, the luminosity rises
strongly right from the onset of collapse which can be considered as a
starting point for the chemical evolution  At the same time disks and
outflows evolve, which should hence have similar time-scales   The
diameter of the shell-like C$_2$H structure in IRAS\,18089-1732 is
$\sim 5''$ (Fig \,\ref{18089}), or $\sim$9000\,AU in radius at the
given distance of 3 6\,kpc   This value is well matched by the modeled
region with decreased C$_2$H abundance (Fig \,\ref{model})   Although
in principle optical depths and/or excitation effects could mimic the
C$_2$H morphology, we consider this as unlikely because the other
observed molecules with many different transitions all peak toward the
central submm continuum emission in IRAS\,18089-1732
\citep{beuther2005c}  Since C$_2$H is the only exception in that rich
dataset, chemical effects appear the more plausible explanation 

The fact that we see C$_2$H at the earliest and the later evolutionary
stages can be explained by the reactive nature of C$_2$H: it is
produced quickly early on and gets replenished at the core edges by
the UV photodissociation of CO  The inner ``chemical'' hole observed
toward IRAS\,18089-1732 can be explained by C$_2$H being consumed in
the chemical network forming CO and more complex molecules like larger
carbon-hydrogen complexes and/or depletion 

The data show that C$_2$H is not suited to investigate the central gas
cores in more evolved sources, however, our analysis indicates that
C$_2$H may be a suitable tracer of the earliest stages of (massive)
star formation, like N$_2$H$^+$ or NH$_3$ (e g ,
\citealt{bergin2002,tafalla2004,beuther2005a,pillai2006})  While a
spatial analysis of the line emission will give insights into the
kinematics of the gas and also the evolutionary stage from chemical
models, multiple C$_2$H lines will even allow a temperature
characterization  With its lowest $J=1-0$ transitions around 87\,GHz,
C$_2$H has easily accessible spectral lines in several bands between
the 3\,mm and 850\,$\mu$m   Furthermore, even the 349\,GHz lines
presented here have still relatively low upper level excitation
energies ($E_u/k\sim42$\,K), hence allowing to study cold cores even
at sub-millimeter wavelengths   This prediction can further be proved
via high spectral and spatial resolution observations of different
C$_2$H lines toward young IRDCs 

\acknowledgments{H B  acknowledges financial support
  by the Emmy-Noether-Programm of the Deutsche Forschungsgemeinschaft
  (DFG, grant BE2578)  }






ground_truth: The focus of the study was on the reactive radical ethynyl (C$_2$H).

prompt_front: Now, answer the following question based on the text below, only give me the answer and do not output any other words.

Question: How do the runtimes and iteration counts of NFPA and FPSA compare to GMRES and DSA in the numerical experiments?

Read the following text and answer briefly.

Context 3: \section{Introduction}\label{sec1}
\setcounter{equation}{0} 

Transport problems with highly forward-peaked scattering are prevalent in a variety of areas, including astrophysics, medical physics, and plasma physics \cite{HGK,aristova,multiphysics} 
For these problems, solutions of the transport equation converge slowly when using conventional methods such as source iteration (SI) \cite{adamslarsen} and the generalized minimal residual method (GMRES) \cite{gmres} 
Moreover, diffusion-based acceleration techniques like diffusion synthetic acceleration (DSA) \cite{alcouffe} and nonlinear diffusion acceleration (NDA) \cite{smithetall} are generally inefficient when tackling these problems, as they only accelerate up to the first moment of the angular flux \cite{JapanFPSA} 
In fact, higher-order moments carry important information in problems with highly forward-peaked scattering and can be used to further accelerate convergence \cite{japanDiss} 

This paper focuses on solution methods for the monoenergetic, steady-state transport equation in homogeneous slab geometry 
Under these conditions, the transport equation is given by
\begin{subequations}\label[pluraleq]{eq1}
\begin{equation}
\label{t1}
\mu\frac{\partial}{\partial x} \psi(x,\mu) + \sigma_t \psi(x,\mu) = \int_{-1}^{1} d\mu' \sigma_s(\mu,\mu') \psi(x,\mu') + Q(x, \mu), \,\,\, x\in [0, X],-1\leq\mu\leq 1  ,\\
\end{equation}
with boundary conditions
\begin{align}
\label{t2}
\psi(0,\mu) &= \psi_L(\mu), \quad \mu > 0,\\
\label{t3}
\psi(X,\mu) &= \psi_R(\mu), \quad \mu < 0 
\end{align}
\end{subequations}
Here, $\psi(x,\mu)$ represents the angular flux at position $x$ and direction $\mu$, $\sigma_t$ is the macroscopic total cross section, $\sigma_s(\mu,\mu')$ is the differential scattering cross section, and $Q$ is an internal source 

New innovations have paved the way to better solve this equation in systems with highly forward-peaked scattering 
For instance, work has been done on modified $P_L$ equations and modified scattering cross section moments to accelerate convergence of anisotropic neutron transport problems \cite{khattab} 
In order to speed up the convergence of radiative transfer in clouds, a quasi-diffusion method has been developed \cite{aristova} 
In addition, the DSA-multigrid method was developed to solve problems in electron transport more efficiently \cite{trucksin} 

One of the most recent convergence methods developed is Fokker-Planck Synthetic Acceleration (FPSA) \cite{JapanFPSA,japanDiss} 
FPSA accelerates up to $N$ moments of the angular flux and has shown significant improvement in the convergence rate for the types of problems described above 
The method returns a speed-up of several orders of magnitude with respect to wall-clock time when compared to DSA  \cite{JapanFPSA} 

In this paper, we introduce a new acceleration technique, called \textit{Nonlinear Fokker-Planck Acceleration} (NFPA) 
This  method  returns  a  modified  Fokker-Planck (FP) equation  that  preserves  the  angular moments of the flux given by the transport  equation 
This preservation of moments is particularly appealing for applications to multiphysics problems \cite{multiphysics}, in which the coupling between the transport physics and the other physics can be done through the (lower-order) FP equation 
To our knowledge, this is the first implementation of a numerical method that returns a Fokker-Planck-like equation that is discretely consistent with the linear Boltzmann equation 

This paper is organized as follows 
\Cref{sec2} starts with a brief description of FPSA 
Then, we derive the NFPA scheme 
In \cref{sec3}, we discuss the discretization schemes used in this work and present numerical results 
These are compared against standard acceleration techniques 
We conclude with a discussion in \cref{sec4} 

\section{Fokker-Planck Acceleration}\label{sec2}
\setcounter{equation}{0} 
In this section we briefly outline the theory behind FPSA, describe NFPA for monoenergetic, steady-state transport problems in slab geometry, and present the numerical methodology behind NFPA 
The theory given here can be easily extended to higher-dimensional problems 
Moreover, extending the method to energy-dependence shall not lead to significant additional theoretical difficulties 

To solve the transport problem given by \cref{eq1} we approximate the in-scattering term in \cref{t1} with a Legendre moment expansion:
\begin{equation}
\label{transport1}
\mu\frac{\partial}{\partial x} \psi(x,\mu) + \sigma_t \psi(x,\mu) = \sum_{l=0}^L \frac{(2l+1)}{2} P_l(\mu) \sigma_{s,l} \phi_l(x) + Q(x, \mu),
\end{equation}
with 
\begin{equation}
\label{transport2}
\phi_l(x) =  \int_{-1}^{1} d\mu P_l(\mu) \psi(x,\mu) 
\end{equation}
Here, $\phi_l$ is the $l^{th}$ Legendre moment of the angular flux, $ \sigma_{s,l}$ is the $l^{th}$ Legendre coefficient of the differential scattering cross section,  and $P_l$ is the $l^{th}$-order Legendre polynomial 
For simplicity, we will drop the notation $(x,\mu)$ in the remainder of this section 

The solution to \cref{transport1} converges asymptotically to the solution of the following Fokker-Planck equation in the forward-peaked limit \cite{pomraning1}:
\begin{equation}
\label{fp1}
\mu\frac{\partial \psi}{\partial x} + \sigma_a \psi = \frac{\sigma_{tr}}{2}\frac{\partial }{\partial \mu} (1-\mu^2) \frac{\partial \psi}{\partial \mu} + Q\,,
\end{equation}
where $\sigma_{tr}= \sigma_{s,0} -\sigma_{s,1}$ is the momentum transfer cross section and $\sigma_a = \sigma_t-\sigma_{s,0}$ is the macroscopic absorption cross section 

Source Iteration \cite{adamslarsen} is generally used to solve \cref{transport1}, which can be rewritten in operator notation:
\begin{equation}
\label{si1}
\mathcal{L} \psi^{m+1} = \mathcal{S} \psi^{m} + Q\,,
\end{equation}
where 
\begin{equation}
\mathcal{L} = \mu \frac{\partial}{\partial x} + \sigma_t,
   \quad
\mathcal{S} = \sum_{l=0}^L \frac{(2l+1)}{2} P_l(\mu) \sigma_{s,l} \int_{-1}^{1}d\mu P_l(\mu) ,
\label{trans1}
\end{equation}
and $m$ is the iteration index 
This equation is solved iteratively until a tolerance criterion is met  The FP approximation shown in \cref{fp1} can be used to accelerate the convergence of \cref{transport1} 

\subsection{FPSA: Fokker-Planck Synthetic Acceleration}\label{FPSA}

In the FPSA scheme \cite{JapanFPSA,japanDiss}, the FP approximation is used as a preconditioner to synthetically accelerate convergence when solving \cref{transport1} (cf  \cite{adamslarsen} for a detailed description of synthetic acceleration) 
When solving \cref{si1}, the angular flux at each iteration $m$ has an error associated with it 
FPSA systematically follows a predict, correct, iterate scheme 
A transport sweep, one iteration in \cref{si1}, is made for a prediction 
The FP approximation is used to correct the error in the prediction, and this iteration is performed until a convergence criterion is met 
The equations used are:
\begin{subequations}
\label{fpsaeq}
\begin{align}
\label{predict}
\mathrm{Predict}&: \mathcal{L} \psi^{m+\frac{1}{2}} = \mathcal{S} \psi^{m} + Q\,,\\
\label{correct}
\mathrm{Correct}&: \psi^{m+1} =  \psi^{m+\frac{1}{2}} + \mathcal{P}^{-1} \mathcal{S} \left( \psi^{m+\frac{1}{2}} -  \psi^{m}\right),
\end{align}
\end{subequations}
where we define $\mathcal{P}$ as
\begin{equation}
\label{FPSAsi1}
\mathcal{P} = \mathcal{A}-\mathcal{F} =\underbrace{\left(\mu\frac{\partial}{\partial x} + \sigma_a\right)}_\mathcal{A} - \underbrace{\left(\frac{\sigma_{tr}}{2}\frac{\partial }{\partial \mu} (1-\mu^2) \frac{\partial }{\partial \mu}\right)}_\mathcal{F},
\end{equation}
In this synthetic acceleration method, the FP approximation is used to correct the error in each iteration of the high-order (HO) equation (\ref{predict})  
Therefore, there is no consistency between the angular moments of the flux in the HO and low-order (LO) equations 

\subsection{NFPA: Nonlinear Fokker-Planck Acceleration}\label{NFPA}

Similar to FPSA, NFPA uses the FP approximation to accelerate the convergence of the solution 
We introduce the additive term $\hat{D}_F$ to \cref{fp1}, obtaining the modified FP equation
\begin{equation}
\label{mfp1}
\mu\frac{\partial \psi}{\partial x} + \sigma_a \psi = \frac{\sigma_{tr}}{2}\frac{\partial }{\partial \mu} (1-\mu^2) \frac{\partial \psi}{\partial \mu} + \hat{D}_F + Q\, 
\end{equation}
The role of $\hat{D}_F$ is to force the transport and modified FP equations to be consistent 
Subtracting \cref{mfp1} from \cref{transport1} and rearranging, we obtain the consistency term
\begin{equation}
\label{dfp}
\hat{D}_F = \sum_{l=0}^L \frac{(2l+1)}{2} P_l \sigma_l \phi_l - \frac{\sigma_{tr}}{2}\frac{\partial}{\partial \mu} (1-\mu^2) \frac{\partial \psi}{\partial \mu} - \sigma_{s,0} \psi\, 
\end{equation}

The NFPA method is given by the following equations:
\begin{subequations}\label[pluraleq]{holocons}
\begin{align}
\label{HO1}
\text{HO}&: \mu\frac{\partial \psi_{HO}}{\partial x} + \sigma_t \psi_{HO} = \sum_{l=0}^L \frac{(2l+1)}{2} P_l \sigma_l \phi_{l, LO} + Q\,,\\
\label{LO11}
\text{LO}&: \mu\frac{\partial \psi_{LO}}{\partial x} + \sigma_a \psi_{LO} = \frac{\sigma_{tr}}{2}\frac{\partial }{\partial \mu} (1-\mu^2) \frac{\partial \psi_{LO}}{\partial \mu} + \hat{D}_F + Q\,,\\
\label{con1}
\text{Consistency term}&: \hat{D}_F = \sum_{l=0}^L \frac{(2l+1)}{2} P_l \sigma_l \phi_{l, HO}^m - \frac{\sigma_{tr}}{2}\frac{\partial }{\partial \mu} (1-\mu^2) \frac{\partial \psi_{HO}}{\partial \mu} - \sigma_{s,0} \psi_{HO}\,,
\end{align}
\end{subequations}
where $\psi_{HO}$ is the angular flux obtained from the HO equation and $\psi_{LO}$ is the angular flux obtained from the LO equation 
The nonlinear HOLO-plus-consistency system given by \cref{holocons} can be solved using any nonlinear solution technique \cite{kelley}  Note that the NFPA scheme returns a FP equation that is consistent with HO transport  
Moreover, this modified FP equation accounts for large-angle scattering which the standard FP equation does not  
The LO equation (\ref{fp1}) can then be integrated into multiphysics models in a similar fashion to standard HOLO schemes \cite{patelFBR}  To solve the HOLO-plus-consistency system above, we use Picard iteration \cite{kelley}:
\begin{subequations}
\begin{align}
\label{H1}
\text{Transport Sweep for HO}&:
\mathcal{L} \psi_{HO}^{k+1} = \mathcal{S} \psi_{LO}^{k} + Q, \\
\label{L1}
\text{Evaluate Consistency Term}&: \hat{D}_F^{k+1} = \left(\mathcal{S} - \mathcal{F} - \sigma_{s,0}\mathcal{I}\right) \psi_{HO}^{k+1}, \\
\label{c1}
\text{Solve LO Equation}&: \psi_{LO}^{k+1} = \mathcal{P}^{-1} \left(\hat{D}_F^{k+1} + Q\right), 
\end{align}
\end{subequations}
where $\mathcal{L}$ and $\mathcal{S}$ are given in \cref{trans1}, $\mathcal{P}$ and $\mathcal{F}$ are given in \cref{FPSAsi1}, $\mathcal{I}$ is the identity operator, and $k$ is the iteration index 
Iteration is done until a convergence criterion is met 

The main advantage of setting up the LO equation in this fashion is that the stiffness matrix for LO needs to be setup and inverted \textit{only once}, just as with FPSA \cite{JapanFPSA, japanDiss}  This has a large impact on the method's performance 
A flowchart of this algorithm is shown in \cref{Nalgorithm} 

\begin{figure}[H]
\centering
\begin{tikzpicture}[node distance = 3cm, auto]
   
    \node [block] (init) {Initial guess of flux moments};
    \node [cloud_HO, right of=init, node distance=4cm] (HOm) {HO};
    \node [cloud_LO, below of=HOm, node distance=2cm] (LOm) {LO};
    \node [HO, below of=init] (transport) {One sweep in transport equation};
    \node [decision, below of=transport,node distance=4cm] (decide) {Flux moments converged?};
    \node [LO, left of=decide, node distance=4cm] (dterm) {Solve for consistency term};
    \node [LO, left of=dterm, node distance=3cm] (MFP) {Solve for FP angular flux};
    \node [LO, above of=MFP, node distance=4cm] (moments) {Convert angular flux to moments};
    \node [block, right of=decide, node distance=4cm] (stop) {Stop};
   
    \path [line] (init) -- (transport);
    \path [line] (transport) -- (decide);
    \path [line] (decide) -- node {no} (dterm);
    \path [line] (dterm) -- (MFP);
    \path [line] (MFP) -- (moments);
    \path [line] (moments) -- (transport);
    \path [line] (decide) -- node {yes}(stop);
\end{tikzpicture}
\caption{NFPA algorithm}
\label{Nalgorithm}
\end{figure}

\section{Numerical Experiments}\label{sec3}

In \cref{sec31} we describe the discretization methods used to implement the algorithms 
In \cref{sec32} we provide numerical results for 2 different choices of source $Q$ and boundary conditions 
For each choice we solve the problem using 3 different scattering kernels, applying 3 different choices of parameters for each kernel 
We provide NFPA numerical results for these 18 cases and compare them against those obtained from FPSA and other standard methods 

All numerical experiments were performed using MATLAB 
Runtime was tracked using the tic-toc functionality \cite{matlab17}, with
only the solver runtime being taken into consideration in the comparisons 
A 2017 MacBook Pro with a 2 8 GHz Quad-Core Intel Core i7 and 16 GB of RAM was used for all simulations 


\subsection{Discretization}\label{sec31}

The Transport and FP equations were discretized using linear discontinuous finite element discretization in space \cite{mpd1}, and discrete ordinates (S$_N$) in angle \cite{landm} 
The Fokker-Planck operator $\mathcal{F}$ was discretized using moment preserving discretization (MPD) \cite{mpd1} 
Details of the derivation of the linear discontinuous finite element discretization can be seen in \cite{japanDiss,martin} 
The finite element discretization for the  Fokker-Planck equation follows the same derivation 

A brief review for the angular discretization used for the FP equation is given below 
First, we use Gauss-Legendre quadrature to discretize the FP equation in angle:
\begin{equation}
\mu_n\frac{\partial \psi_n(x)}{\partial x} + \sigma_a \psi_n(x) - \frac{\sigma_{tr}}{2}\nabla^2_n \psi_n(x) =  Q_n(x),
\end{equation}
for $n=1,  ,N$ 
Here, $\nabla^2_n$ term is the discrete form of the angular Laplacian operator evaluated at angle $n$ 

The MPD scheme is then shown as
\begin{equation}
\nabla^2_n \psi_n = M \psi_n = V^{-1} L V \psi_n,
\end{equation}
where $M$ is the MPD discretized operator defined by
\begin{subequations}
\begin{equation}
V_{i,j} = P_{i-1}(\mu_j)w_j,
\end{equation}
and 
\begin{equation}
L_{i,j} = -i(i-1),
\end{equation}
\end{subequations}
for $i,j=1,   ,N$ 
Here, $P_l(\mu_j)$ are the Legendre polynomials evaluated at each angle $\mu_j$ and $w_j$ are the respective weights 
$M$ is defined as a (N x N) operator for a vector of $N$ angular fluxes $ \psi(x)$, at spatial location $x$  

In summary, if we write the FP equation as
\begin{equation}
\mathcal{H} \frac{\partial \psi}{\partial x}(x) + \sigma_a \psi(x) - \mathcal{F} \psi(x) =  Q(x),
\end{equation}
then $\mathcal{H}$ is Diag$(\mu_n)$ for $n=1,   ,N$, $Q(x)$ is a vector of source terms $Q_n(x)$, and $\mathcal{F}$ is represented by $\frac{\sigma_{tr}}{2}M$ 


\subsection{Numerical Results}\label{sec32}

It is shown that for slowly converging problems, typical convergence methods like $L_\infty$ suffer from false convergence \cite{adamslarsen} 
To work around this issue, the criterion is modified to use information about the current and previous iteration:
\begin{equation}
\label{falseconverge}
\frac{|| \phi^{m}_0(x) - \phi^{m-1}_0(x) ||_2}{1-\frac{|| \phi^{m+1}_0(x) - \phi^{m}_0(x) ||_2}{|| \phi^{m}_0(x) - \phi^{m-1}_0(x) ||_2}} < 10^{-8} 
\end{equation}

Two problems were tested using 200 spatial cells, $X$ = 400, $\sigma_a = 0$, $L$ = 15, and $N$ = 16 
Problem 1 has vacuum boundaries and a homogeneous isotropic source $Q$ for $0 < x < X$ 
Problem 2 has no internal source and an incoming beam at the left boundary  The source and boundary conditions used are shown in \cref{parameters}  
\begin{table}[H]
\begin{center}
\scalebox{0 9}{
\begin{tabular}{c | c | c} \hline 
& Problem 1 & Problem 2 \\ \hline \hline
Q(x) & 0 5 & 0 \\
$\psi_L$ & 0 & $\delta(\mu - \mu_N)$  \\
$\psi_R$ & 0 & 0 \\
\end{tabular}}
\end{center}
\caption{Problem Parameters}
\label{parameters} 
\end{table} 
We consider three scattering kernels in this paper: Screened Rutherford \cite{pomraning1}, Exponential \cite{pomraning2}, and Henyey-Greenstein \cite{HGK} 
Three cases for each kernel were tested 
The results obtained with NFPA are compared with those obtained using GMRES, DSA, and FPSA with the MPD scheme 

\subsubsection{SRK: Screened Rutherford Kernel}

The Screened Rutherford Kernel \cite{pomraning1, JapanFPSA} is a widely used scattering kernel for modeling scattering behavior of electrons \cite{SRK} 
The kernel depends on the parameter $\eta$, such that
\begin{equation}
\sigma^{SRK}_{s,l} = \sigma_s  \int_{-1}^{1} d\mu P_l(\mu) \frac{\eta (\eta+1)}{(1+2\eta-\mu)^2} 
\end{equation}
The SRK has a valid FP limit as $\eta$ approaches 0 \cite{patelFBR}  Three different values of $\eta$ were used to generate the scattering kernels shown in \cref{SRK} 
GMRES, DSA, FPSA, and NFPA all converged to the same solution for problems 1 and 2  \Cref{SRK_plots} shows the solutions for SRK with $\eta = 10^{-7}$ 
\begin{figure}[t]
\begin{center}
  \includegraphics[scale=0 1,angle=0]{SRK jpg}
  \caption{Screened Rutherford Kernels}
  \label{SRK}
\end{center}
\end{figure}
\begin{figure}[H]
    \centering
    \subfloat[Problem 1]{{\includegraphics[width=7cm]{s7_iso jpg} }}
    \qquad
    \subfloat[Problem 2]{{\includegraphics[width=7cm]{s7_beam jpg} }}
    \caption{Results for SRK Problems with $\eta = 10^{-7}$}
    \label{SRK_plots}
\end{figure}

\begin{table}[H]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$\eta = 10^{-5}$} & GMRES & 98 8 & 12 \\
& DSA & 2380 & 53585 \\
& FPSA & 1 21 & 26 \\
& NFPA & 1 39 & 26 \\ \hline 
\multirow{4}{*}{$\eta = 10^{-6}$} & GMRES & 208 & 84 \\
& DSA & 3040 & 69156 \\
& FPSA & 0 747 & 16 \\
& NFPA & 0 857 & 16 \\ \hline 
\multirow{4}{*}{$\eta = 10^{-7}$} & GMRES & 174 & 124 \\
& DSA & 3270 & 73940 \\
& FPSA & 0 475 & 10 \\
& NFPA & 0 542 & 10 \\ \hline
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 1 with SRK}
\label{SRKresults1} 
\end{table}
\begin{table}[H]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$\eta = 10^{-5}$} & GMRES & 52 4 & 187 \\
& DSA & 1107 & 25072 \\
& FPSA & 0 953 & 20 \\
& NFPA & 1 14 & 20 \\ \hline 
\multirow{4}{*}{$\eta = 10^{-6}$} & GMRES & 108 & 71 \\
& DSA & 1434 & 32562  \\
& FPSA & 0 730 & 14 \\
& NFPA & 0 857 & 14 \\ \hline 
\multirow{4}{*}{$\eta = 10^{-7}$} & GMRES & 94 1 & 185 \\
& DSA & 1470 & 33246 \\
& FPSA & 0 438 & 8 \\
& NFPA & 0 484 & 8 \\ \hline  
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 2 with SRK}
\label{SRKresults2} 
\end{table}

The results of all solvers are shown in \cref{SRKresults1,SRKresults2} 
We see that NFPA and FPSA tremendously outperform GMRES and DSA in runtime for all cases 
FPSA is a simpler method than NFPA, requiring less calculations per iteration; therefore, it is expected that it outperforms NFPA in runtime 
We see a reduction in runtime and iterations for FPSA and NFPA as the FP limit is approached, with DSA and GMRES requiring many more iterations by comparison as $\eta$ approaches 0 

An advantage that NFPA offers is that the angular moments of the flux in the LO equation will remain consistent with those of the transport equation even as a problem becomes less forward-peaked 
On the other hand, the moments found using only the FP equation and source iteration lose accuracy 
To illustrate this, Problem 1 was tested using different Screened Rutherford Kernels with increasing $\eta$ parameters 
The percent errors (relative to the transport solution) for the scalar flux obtained with the LO equation and with the standard FP equation at the center of the slab are shown in \cref{momcomp} 
It can be seen that the percent relative errors in the scalar flux of the FP solution is orders of magnitude larger than the error produced using the LO equation 
The same trend can be seen when using the exponential and Henyey-Greenstein kernels  

\begin{figure}[H]
\begin{center}
  \includegraphics[scale=0 15,angle=0]{relerrorlog jpg}
  \caption{Log Scale of $\%$ Relative Error vs $\eta$ for Problem 1 at the Center of the Slab with SRK}
  \label{momcomp}
\end{center}
\end{figure}

\subsubsection{EK: Exponential Kernel}

The exponential kernel \cite{pomraning2, JapanFPSA} is a fictitious kernel made for problems that have a valid Fokker-Planck limit \cite{pomraning1} 
The zero$^{\text{th}}$ moment, $\sigma^{EK}_{s,0}$, is chosen arbitrarily; we define $\sigma^{EK}_{s,0}$ as the same zero$^{\text{th}}$ moment from the SRK 
The $\Delta$ parameter determines the kernel: the first and second moments are given by 
\begin{subequations}
\begin{align}
\sigma^{EK}_{s,1} &= \sigma^{EK}_{s,0} (1-\Delta),\\
\sigma^{EK}_{s,2} &= \sigma^{EK}_{s,0} (1-3\Delta+3\Delta^2),
\end{align}
and the relationship for $l\geq 3$ is
\begin{equation}
\sigma^{EK}_{s,l} = \sigma^{EK}_{s,l-2} - \Delta(2l+1) \sigma^{EK}_{s,l-1} 
\end{equation}
\end{subequations}
As $\Delta$ is reduced, the scattering kernel becomes more forward-peaked 

The EK has a valid FP limit as $\Delta$ approaches 0 \cite{patelFBR} 
Three different values of $\Delta$ were used to generate the scattering kernels shown in \cref{EXP} 
The generated scattering kernels are shown in \cref{EXP} 
GMRES, DSA, FPSA, and NFPA all converged to the same solution for problems 1 and 2 
\Cref{EK_plots} shows the solutions for EK with $\Delta = 10^{-7}$ 
\begin{figure}[t]
\begin{center}
  \includegraphics[scale=0 1,angle=0]{EXP jpg}
  \caption{Exponential Kernels}
  \label{EXP}
\end{center}
\end{figure}
\begin{figure}[H]
    \centering
    \subfloat[Problem 1]{{\includegraphics[width=7cm]{dta7_iso jpg} }}
    \qquad
    \subfloat[Problem 2]{{\includegraphics[width=7cm]{dta7_beam jpg} }}
    \caption{Results for EK Problems with $\Delta = 10^{-7}$}
    \label{EK_plots}
\end{figure}

The runtimes and iterations for GMRES, DSA, FPSA, and NFPA are shown in \cref{Expresults1,Expresults2} 
We see a similar trend with the EK as seen with SRK 
Smaller $\Delta$ values lead to a reduction in runtime and iterations for NFPA and FPSA, which greatly outperform DSA and GMRES in both categories 

\begin{table}[h]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$\Delta = 10^{-5}$} & GMRES & 196 & 142 \\
& DSA & 3110 & 70140 \\
& FPSA & 0 514 & 11 \\ 
& NFPA & 0 630 & 11 \\\hline 
\multirow{4}{*}{$\Delta = 10^{-6}$} & GMRES & 156 & 132 \\
& DSA & 3120 & 70758 \\
& FPSA & 0 388 & 7 \\ 
& NFPA & 0 393 & 7 \\ \hline 
\multirow{4}{*}{$\Delta = 10^{-7}$} & GMRES & 81 & 127 \\
& DSA & 3120 & 70851  \\
& FPSA & 0 292 & 6 \\ 
& NFPA & 0 318 & 6 \\ \hline
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 1 with EK}
\label{Expresults1} 
\end{table}
\begin{table}[h]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$\Delta = 10^{-5}$} & GMRES & 110 & 73 \\
& DSA & 1455 & 33033 \\
& FPSA & 0 492 & 10 \\ 
& NFPA & 0 613 & 10 \\ \hline 
\multirow{4}{*}{$\Delta = 10^{-6}$} & GMRES & 82 7 & 79 \\
& DSA & 1470 & 33309 \\
& FPSA & 0 358 & 7 \\ 
& NFPA & 0 431 & 7 \\ \hline 
\multirow{4}{*}{$\Delta = 10^{-7}$} & GMRES & 56 8 & 90 \\
& DSA & 1470 & 33339 \\
& FPSA & 0 273 & 5 \\ 
& NFPA & 0 319 & 5 \\ \hline  
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 2 with EK}
\label{Expresults2} 
\end{table}

\subsubsection{HGK: Henyey-Greenstein Kernel}

The Henyey-Greenstein Kernel \cite{HGK,JapanFPSA} is most commonly used in light transport in clouds 
It relies on the anisotropy factor $g$, such that
\begin{equation}
\sigma^{HGK}_{s,l} = \sigma_s g^l 
\end{equation}
As $g$ goes from zero to unity, the scattering shifts from isotropic to highly anisotropic 
\begin{figure}[H]
\begin{center}
  \includegraphics[scale=0 1,angle=0]{HGK jpg}
  \caption{Henyey-Greenstein Kernels}
  \label{HGK}
\end{center}
\end{figure}
\begin{figure}[H]
    \centering
    \subfloat[Problem 1]{{\includegraphics[width=7cm]{g099_iso jpg} }}
    \qquad
    \subfloat[Problem 2]{{\includegraphics[width=7cm]{g099_beam jpg} }}
    \caption{Results for HGK Problems with $g = 0 99$}
    \label{HGK_plots}
\end{figure}


The HGK does not have a valid FP limit \cite{patelFBR} 
The three kernels tested are shown in \cref{HGK} 
GMRES, DSA, FPSA, and NFPA all converged to the same solution for problems 1 and 2 
\Cref{HGK_plots} shows the solutions for HGK with $g = 0 99$ 
The results of each solver are shown in \cref{HGKresults1,HGKresults2}  
\begin{table}[h]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$g=0 9$} & GMRES & 9 88 & 76 \\
& DSA & 24 5 & 554 \\
& FPSA & 1 50 & 32 \\ 
& NFPA & 1 39 & 27 \\ \hline 
\multirow{4}{*}{$g=0 95$} & GMRES & 12 2 & 131 \\
& DSA & 47 7 & 1083 \\
& FPSA & 1 75 & 38 \\ 
& NFPA & 1 83 & 35 \\ \hline 
\multirow{4}{*}{$g=0 99$} & GMRES & 40 0 & 27 \\
& DSA & 243 & 5530  \\
& FPSA & 3 38 & 74 \\ 
& NFPA & 3 93 & 73 \\ \hline
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 1 with HGK}
\label{HGKresults1} 
\end{table}
\begin{table}[h]
\begin{center}
\scalebox{0 8}{
\begin{tabular}{c || c || c || c} \hline 
Parameter & Solver & Runtime (s) & Iterations \\ \hline \hline
\multirow{4}{*}{$g=0 9$} & GMRES & 24 3 & 135 \\
& DSA & 14 8 & 336  \\
& FPSA & 1 15 & 23 \\ 
& NFPA & 1 35 & 24 \\ \hline 
\multirow{4}{*}{$g=0 95$} & GMRES & 31 3 & 107 \\
& DSA & 29 7 & 675 \\
& FPSA & 1 56 & 32 \\ 
& NFPA & 1 90 & 33 \\ \hline 
\multirow{4}{*}{$g=0 99$} & GMRES & 41 4 & 126 \\
& DSA & 146 & 3345 \\
& FPSA & 3 31 & 67 \\ 
& NFPA & 3 99 & 67 \\ \hline  
\end{tabular}}
\end{center}
\caption{Runtime and Iteration Counts for Problem 2 with HGK}
\label{HGKresults2} 
\end{table}

Here we see that NFPA and FPSA do not perform as well compared to their results for the SRK and EK 
Contrary to what happened in those cases, both solvers require more time and iterations as the problem becomes more anisotropic 
This is somewhat expected, due to HGK not having a valid Fokker-Planck limit 
However, both NFPA and FPSA continue to greatly outperform GMRES and DSA 
Moreover, NFPA outperforms FPSA in iteration count for problem 1 


\section{Discussion}\label{sec4}

This paper introduced the Nonlinear Fokker-Planck Acceleration technique for steady-state, monoenergetic transport in homogeneous slab geometry 
To our knowledge, this is the first nonlinear HOLO method that accelerates \textit{all $L$ moments} of the angular flux 
Upon convergence, the LO and HO models are consistent; in other words, the (lower-order) modified Fokker-Planck equation \textit{preserves the same angular moments} of the flux obtained with the (higher-order) transport equation 

NFPA was tested on a homogeneous medium with an isotropic internal source with vacuum boundaries, and in a homogeneous medium with no internal source and an incoming beam boundary 
For both problems, three different scattering kernels were used 
The runtime and iterations of NFPA and FPSA were shown to be similar 
They both vastly outperformed DSA and GMRES for all cases by orders of magnitude 
However, NFPA has the feature of preserving the angular moments of the flux in both the HO and LO equations, which offers the advantage of integrating the LO model into multiphysics models  

In the future, we intend to test NFPA capabilities for a variety of multiphysics problems and analyze its performance 
To apply NFPA to more realistic problems, it needs to be extended to include time and energy dependence  
Additionally, the method needs to be adapted to address geometries with higher-order spatial dimensions 
Finally, for the NFPA method to become mathematically ``complete", a full convergence examination using Fourier analysis must be performed 
However, this is beyond the scope of this paper and must be left for future work 

\section*{Acknowledgements}

The authors acknowledge support under award number NRC-HQ-84-15-G-0024 from the Nuclear Regulatory Commission 
The statements, findings, conclusions, and recommendations are those of the authors and do not necessarily reflect the view of the U S  Nuclear Regulatory Commission 

J ~K  Patel would like to thank Dr ~James Warsa for his wonderful transport class at UNM, as well as his synthetic acceleration codes 
The authors would also like to thank Dr ~Anil Prinja for discussions involving Fokker-Planck acceleration 







ground_truth: NFPA and FPSA greatly outperform GMRES and DSA.