# Spectroscopy and Mass-spectrometry in Physical and Analytical Chemistry of Biological Systems and Industrial Products

Roman M Balabin

► To cite this version:

Roman M Balabin. Spectroscopy and Mass-spectrometry in Physical and Analytical Chemistry of Biological Systems and Industrial Products. Doctoral. Applied plasma chemistry, Nanchang, China. 2023, pp.55. hal-05136987

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https://hal.science/hal-05136987v1

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# Spectroscopy and Mass-spectrometry in Physical and Analytical Chemistry of Biological Systems and Industrial Products

Roman M. Balabin, PhD

BWAN – BrainWare Analytics, Zurich, Switzerland

BSH – Bond Street Holdings, Charlestown, Nevis
# Outline

**Part I. Bio / CV**

**Part II. Results:**
Petroleum macromolecules and
surface science

**Part II. BrainWare Analytics GmbH**

**Part III. The HyDRA Challenge**

**Part IV. Triplets (de)activation**

**Part V. Above the ground(state)**

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# Part I. Bio / CV
Early Years: 1985–2002

* Name: **Roman M. Balabin** (Роман Балабин)

* ORCID: [0000-0001-9374-1809](https://orcid.org/0000-0001-9374-1809)

* ResearcherID: [M-7662-2019](https://researcherid.com/ru/M-7662-2019)

* Scopus ID: [15049329900](https://scopus.com/scopus/ search?view=详情&text=15049329900)

* Born on August 21, 1985, in the Cheryomushki (Brezhnevsky) district of **Moscow**, USSR

* Family:

* Mother: Irina V. Balabina (Ivanova; 1960, Moscow)

* Father: Mikhail I. Balabin (Shegidevich; 1961, Moscow)

* Grandfather: Izmail Yakovlevich Shegidevich (Izmail Jakubowicz Szegidewicz) – repressed nobleman of Polish-Tatar origin

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<figure><img src="image_5.png" /></figure>
Early Years: 1985–2002

* Lived on Khersonskaya and Volgina str. (Moscow)

* Summer vacations in **Spassk** (Bednodemyanovsk) of Penza Oblast, especially in 1992–1994

* Shortly lived in **Anapa** (Kuban, 1988–1989), **Pyatigorsk** (Stavropolye, 1990), **Sochi** (1991) and **Tallin** (1990–1991)

* First travel to Western Europe, **Rome**, in Aug 1995

* Moved to **Blaibach** (Oberpfalz, Bayern, Germany) in 1996–1997

* Lived in **Zandt** (Oberpfalz, Bayern) in 1998

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# School Education

* Primary school No. 1655 / No. 15 (Khersonskaya, Moscow)

* School No. 562 / No. 15 (Perekopskaya, Moscow)

* School No. 1073 (Varshavskoe, Moscow) with its program authored by **Vladimir Myskin**

* Information Technology Lyceum No. 1533 “LIT” (Lomonosovsky) from 2000 to 2002 – **UNESCO Associated Schools Project Network (ASPnet)**

* Computer science, math and IT

* Diploma thesis with **Aleksandr Giglavyj**: “Information and communication technology (ICT) market of the Baltic states” (2002)

<figure><img src="image_8.png" /></figure>

United Nations
Educational, Scientific and
Cultural Organization

<figure><img src="image_9.png" /></figure>

UNESCO Associated Schools

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University Years: 2002–2008

* Uni: **Gubkin University** of Oil and Gas (Moscow)

• Faculty of Chemical Engineering and Ecology

• Department of Organic Chemistry and Petrochemistry

* Major: chemistry and technology of **natural gas**

* Scientific collaborations:

• Bruker Optics (Bremen, Germany)

• ITERA / ARETI Group (Geneva, Switzerland)

• Department of Physics, **Umea University** (Sweden)

* Institute of Problems of Chemical Physics
  (Chernogolovka, Moscow Oblast)

- Nesmeyanov Institute of Organoelement Compounds

<figure><img src="image_11.png" /></figure>
University Years: 2002–2008

* Uni: **Gubkin University** of Oil and Gas (Moscow)

• Faculty of Chemical Engineering and Ecology

• Department of Organic Chemistry and Petrochemistry

* Major: chemistry and technology of **natural gas**

* Industrial partners:

• Lumex Instruments (St. Petersburg)

• Orsknefteorgsintez / RussNeft (Orenburg Oblast)

• Kirishinefteorgsintez / Kinef (Leningrad Oblast)

• Astrakhan Gas Processing Plant / Gazprom

• Kuibyshevsky Refinery (Samara Oblast)

• The Ryazan Refinery / TNK-BP (Ryazan Oblast)

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Pre-doc Studies: 2007–2008

* Georg August University of Göttingen (Germany)

* Institute of Physical Chemistry

* Graduate school: Spectroscopy of molecular aggregates (GRK 782 PCGG, GEPRIS 273443)

* Group of Prof. Dr. **Martin Suhm** / Philipp Zielke

* Topic: Raman spectroscopy of normal alkanes

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* Ruprecht Karl University of Heidelberg (Germany)

* Institute of Applied Physical Chemistry

* Group of Prof. Dr. **Michael Grunze** / Patrick Koelsch

* Topic: sum-frequency-generation spectroscopy (SFGS) of biofilms

<figure><img src="image_15.png" /></figure>
# Pre-doc Studies: 2007–2008

* University of Basel (Switzerland)

* Department of Chemistry

* Group of Prof. Dr. John Paul Maier / Egor Chasovskikh

* Topic: electronic spectroscopy of carbon radicals and ions (SNSF 115864)

* Theoretical calculations: Université Paris-Est, Laboratoire de Chimie Théorique (France)

* Max Planck Institute for Polymer Research in Mainz

* Experimental Physics of Interfaces @ MPI-P

* Group of Prof. Dr. Hans-Jurgen Butt / Gunter Auernhammer

* Invited talk on physical chemistry and spectroscopy of petroleum macromolecules

<figure><img src="image_16.png" /></figure>

Universität
Basel

Max-Planck-Institut
für Polymerforschung

Max Planck Institute
for Polymer Research

<figure><img src="image_17.png" /></figure>
PhD Studies: 2008–2012

* Uni: ETH Zurich (Switzerland)

* Department of Chemistry and Applied Biosciences (D-CHAB)

* Group of Prof. Dr. Renato Zenobi

* Vibrational spectroscopy and mass-spectrometry

* PhD thesis: "Development of express methods for analysis of petroleum refining products and petrochemicals based on vibrational spectroscopy" (Gubkin University, 2013)

<figure><img src="image_18.png" /></figure>

* Industrial partners:

* Danone Research Centre Daniel Carasso (Paris)

* Unimilk (Moscow Oblast)

* NT-MDT (Zelenograd, Moscow)
Part II. Results
Petroleum macromolecules and surface science
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# Dielectric spectroscopy: permittivity

* Dielectric spectroscopy of oil:

* Paper "Frequency Dependence of Oil Conductivity at High Pressure" (2007)

* Method: Dielectric spectroscopy (DS, impedance spectroscopy)

* DS measures the dielectric properties of a medium as a function of applied frequency.

* DS is based on the interaction of an external field with the electric **dipole moment** of the sample.

* The result is expressed by **complex permittivity**.

<figure><img src="image_20.png" /></figure>

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<figure><img src="image_22.png" /></figure>

# Dielectric spectroscopy: model

## Dielectric spectroscopy of oil:

* Paper "Frequency Dependence of Oil Conductivity at High Pressure" (2007)

* Samples:

* Toluene solutions of asphaltene

* Concentration of 0.3% (2.7 g/L) and 3% mass. (27 g/L)

* Conditions:

* Temperatures of 312 and 294 K

* Pressure: 0.1–1.0 GPa

* Model:

$$ \frac{\varepsilon^* - \varepsilon_\infty}{A(i\omega)^n - \varepsilon_\infty} = (1 + i\omega\tau)^{-1} $$

* Alternative to Jonscher's "universal dielectric response" (UDR, 1977).

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# Fluorescence anisotropy

## Fluorescence polarization of asphaltenes:

* Paper "Polarization of Fluorescence of Asphaltene Containing Systems" (2008)

* Method: Fluorescence spectroscopy (fluorimetry or spectrofluorometry)

* A complementary technique is absorption spectroscopy.

* Oil fluorophores are asphaltenes as they contain several combined aromatic groups.

* Anisotropy by Levshin for monodispersed systems:

$$ \left(1 - \frac{3}{2}\sin^2\xi\right) \left(\frac{1}{P} - \frac{1}{3}\right) = \frac{1}{P_0} - \frac{1}{3} $$

<figure><img src="image_26.png" /></figure>
<figure><img src="image_27.png" /></figure>

# Fluorescence anisotropy

## Fluorescence polarization of asphaltenes:

* Paper "Polarization of Fluorescence of Asphaltene Containing Systems" (2008)

### Sample:

* Asphaltenes in CCl₄ or toluene

* Light catalytic gasoil, LCG

* Distillate cracking residue, RCD

* Anisotropy for polydisperse (nonuniform) systems:

$$ \frac{1}{P} = \frac{1}{3} + \left(\frac{1}{P_0} - \frac{1}{3}\right) \frac{\int \omega_V(V) dV}{\int \frac{V \omega_V(v) dV}{\frac{\tau k T}{\eta} + V}} = \frac{1}{3} + \left(\frac{1}{P_0} - \frac{1}{3}\right) \frac{1}{S} $$

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# Dipole Moment of Fractal Cluster

* **Molecular dynamics** of asphaltenes:

* Paper "Calculation of Dipole Moment of Fractal Asphaltene Cluster" (2011)

* Method: **diffusion-limited aggregation** (DLA)

* a random walk due to Brownian motion and a cluster process to form fractal aggregates

* Diffusion is the primary means of transport.

* Mansoori and colleagues have created a model based on the concept of fractal structure of asphaltene clusters.

<figure><img src="image_31.png" /></figure>
<figure><img src="image_32.png" /></figure>

# Dipole Moment of Fractal Cluster

## Molecular dynamics of asphaltenes:

* Paper “Calculation of Dipole Moment of Fractal Asphaltene Cluster” (2011)

### System:

* petroleum pitch – as it possesses paramagnetic properties

* The dipole moment of the asphaltene cluster was demonstrated to vary according to **power law** in relation to the cluster mass.

* The dipole-dipole interactions between the asphaltene nanoaggregates increase.

* Analytical solution:

$$p_N = p_0 \cdot N^\beta; \quad \beta = \frac{4}{15} \cdot \frac{p_0^2}{4\pi\varepsilon_0\varepsilon k_B T r_0^3}$$

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Other Results
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# Scientific and industrial results

* Machine learning for vibrational spectroscopy data:

* A series of papers on near-infrared spectroscopy of petrochemicals, products of petroleum refining and biofuels:

* Fuel (2007) 323, Energy Fuels (2007) 2460, Chemom Intell Lab Syst (2007) 183, Fuel (2008) 1096, Chemom Intell Lab Syst (2008) 58, Fuel (2008) 2745, Neural Comput Appl (2009) 557, ACA (2010) 27, Analyst (2011) 1703, ACA (2011) 190, ACA (2011) 63, Fuel (2011) 2007, Microchem J (2011) 121, Energy Fuels (2011) 2373, Analyst (2012) 1604.

* Practical implementation for laboratory analysis at Kinef (Kirishi), Samara, Gazprom (Astrakhan) and Mozyr Refinery (Belarus)

* Petroleum macromolecules and surface science:

* A series of papers on asphaltenes, petroleum resins and other colloid systems:

* JDST (2007) 419, JNIRS (2007) 343, JDST (2008) 457, JCIS (2008) 167, JDST (2008) 1505, Energy Fuels (2009) 1230, Energy Fuels (2011) 189, JDST (2011) 1502, Phys Wave Phen (2015) 143.

* Colloid state control of Kumkol oil (Kazakhstan)
<figure><img src="image_36.png" /></figure>

Scientific and industrial results

* Physical chemistry of normal alkanes:

* A series of papers on quantum chemistry and Raman spectroscopy of alkanes:

* *Chem Phys (2008) 267*, *JCP (2008) 164101*, *JPCA (2009) 1012*, *JPCA (2010) 6729*, *Mol Phys (2011) 943*.

* The **benchmark** experimental value for the enthalpy difference between *trans* and *gauche* conformations of normal butane: $\Delta H = 660 \pm 22 \text{ cal mol}^{-1}$

* Used by Bachrach in *Computational Organic Chemistry* (2014), Vogel & Houk in *Organic Chemistry* (2019), AMBER FF for biomolecules, etc.

* Machine learning for quantum chemistry:

* One of the **earliest** attempts to combine ML and QC:

* *JCP (2009) 074104*, *PCCP (2011) 11710*.

* Almost zero interest after publication, but became a large separate field of studies in 2020s: ML-DFT, ML-FF, $\Delta$-learning, etc.

* Review by Dral in *Quantum Chemistry in the Age of Machine Learning* (2022) 698 pp.
<figure><img src="image_37.png" /></figure>

Scientific and industrial results

* Physical chemistry of **biomolecules**:

* A series of papers on QC and Raman spectroscopy of gas-phase **amino acids**:

* *Chem Phys Lett* (2009) 195, *PCCP* (2010) 5980, *JPCL* (2010) 20, *JCP* (2010) 231101, *JPCB* (2010) 15075, *Comput Theor Chem* (2011) 15, *PCCP* (2012) 99.

* The very first measurement of **conformation equilibrium in free glycine**

* QC of other biomolecules – triazoles, tetrazole, formic acid, aldehydes, etc.:

* *JCP* (2009) 154307, *JPCA* (2009) 4910, *JPCA* (2010) 3698, *JCP* (2010) 211103, *JASMS* (2011) 1167, *Struct Chem* (2011) 1047, *Mol Phys* (2011) 2341, *PCCP* (2023) 22089.

* **Mass-spectrometry and electronic spectroscopy:**

* Food samples, dyes, peptides, biocomplexes, etc.:

* *Analyst* (2010) 773, *PCCP* (2010) 11710, *PCCP* (2010) 14121, *JASMS* (2010) 172, *Angewandte* (2010) 2358, *Anal Chem* (2010) 7394, *ABC* (2010) 405, *IJMS* (2011) 241, *RSCA* (2011) 1962.

* Proof that electrospray ionization (ESI) generates **gaseous analytes at ambient conditions**
# Journalist

• Business-Swiss, Zurich

• Edited by Marad Widmer, LL.M.

• Shveytsariya Delovaya / Widmer Strategy GmbH

Известия Деловаа

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НАША
ГАЗЕТА

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• Nasha Gazeta, Geneva

• Edited by Dr. Nadia Sikorsky (Nadezhda Sikorskaya)

• Interview with brigadier Fredy Keller (SWISSINT)

• Wikinews, Miami, FL

• Interviews with Profs. Jonathan Gruber (MIT), Clive Spash (CSIRO), Stephen Ward (UBC), Robert Costanza (UCL)

<figure><img src="image_40.png" /></figure>

WIKINEWS
Part II. BrainWare Analytics GmbH
# BrainWare Analytics: formal

* Formal: **Brainware Analytics GmbH** (Switzerland)

* BrainWare Analytics LLC (BWAN)

* EU VAT: CHE-202.748.777

* Commercial register CH-170.4.011.342-9

* Statutory date: 10 Jul 2012

* Daily register No. 9743 / Publication number: 6791860

* Official address: Rathausstrasse 14, 6340 Baar, Zug

* Industry: computer hardware, provision of IT services

* Share capital: 20'000 CHF

* Registered persons: "Balabin, Roman, Russian citizen, in Schlieren, managing director, with sole signature and shareholder" (SHAB)
# BrainWare Analytics: locations

* Office in Schlieren, 2013–2014:

* Address: Grabenstrasse 11a, 8952 Schlieren, Zurich

* Partner: Dualsystems Biotech AG

* proteomics for industry and academia

* Office at Technopark Zurich, 2014–2017:

* Address: Newton 1.OG, Technopark Zurich, Technoparkstrasse 1, 8005 Industriequartier, Zurich

* Five people in Jul 2014:

* two scientists with PhDs, two computer engineers and an expert in GPU-based computer simulations

* “Balabin, Roman, Russian citizen, in Schlieren, managing director, with sole signature and shareholder... Kornilov, Pavel, Russian citizen, in Zurich, shareholder, without signatory power” (SHAB)

<figure><img src="image_41.png" /></figure>

<figure><img src="image_42.png" /></figure>
# General-purpose computing on GPUs

* GPGPU = the use of a graphics processing units (GPUs) beyond computation of computer graphics only

* GPUs could perform computation in applications traditionally handled by the central processing unit (CPU)

* Fits scientific computing

* The use of multiple video cards in one computer further parallelizes the processing

<figure><img src="image_43.png" /></figure>
# General-purpose computing on GPUs

* GPGPU = the use of a graphics processing units (GPUs) beyond computation of computer graphics only

* GPUs could perform computation in applications traditionally handled by the central processing unit (CPU)

* Fits scientific computing

* Example: estimation of non-linear parameters by the Levenberg-Marquardt algorithm

<figure><img src="image_44.png" /></figure>
# Part III. The HyDRA Challenge
# The HyDRA Challenge

<figure><img src="image_45.png" /></figure>

* Hydrate Donor Redshift Anticipation (HyDRA) blind challenge for the microhydration

* Organizers:

* University of Göttingen / Paris-Saclay University

* Prof. Dr. **Ricardo Mata** (theor) / Prof. Dr. **Anne Zehnacker-Rentien** (exp)

* Ten complexes of organic molecules with water

* No experimental information prior to predictions' submission (before Mar 2022)

<figure><img src="image_46.png" /></figure>

ACE: 67-64-1

<figure><img src="image_47.png" /></figure>

IMZ: 288-32-4

<figure><img src="image_48.png" /></figure>

CBU: 1191-95-3

<figure><img src="image_49.png" /></figure>

ANL: 62-53-3

<figure><img src="image_50.png" /></figure>

OCP: 611-20-1

<figure><img src="image_51.png" /></figure>

APH: 98-86-2

<figure><img src="image_52.png" /></figure>

POH: 98-85-1

<figure><img src="image_53.png" /></figure>

TFB: 327-54-8

<figure><img src="image_54.png" /></figure>

DBN: 2406-25-9

<figure><img src="image_55.png" /></figure>

DBF: 132-64-9
# The HyDRA Challenge

<figure><img src="image_56.png" /></figure>

* The role of theory in understanding hydration is multifaceted:

* Helps to **assign** the experimental spectral data

* Could even **replace** experiment (to some extent)

* A need for **unbiased** tests of different predictive theoretical approaches by experiment

<figure><img src="image_57.png" /></figure>
# The HyDRA Challenge: structures

<figure><img src="image_58.png" /></figure>

* The role of theory in understanding hydration is multifaceted:

* Helps to **assign** the experimental spectral data

* Could even **replace** experiment (to some extent)

* A need for **unbiased** tests of different predictive theoretical approaches by experiment
The HyDRA Challenge: structures

<figure><img src="image_59.png" /></figure>

* To predict the **hydrogen-bonded** OH bond stretching fundamental of water in clusters

* Relative to the free water value of app. 3657 cm⁻¹

* Experimental **symmetric stretch**

* Starting date of Phase I: Feb 2021

* The official start: 24 Aug 2021
Part IV. Triplets (de)activation
# Singlet states vs Triplet states

* **Clebsch-Gordan coefficients:**

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\uparrow), $$

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\downarrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\uparrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\downarrow) $$

* There are three states with total spin angular momentum of one

<figure><img src="image_60.png" /></figure>
# Singlet states vs Triplet states

* **Clebsch-Gordan coefficients:**

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\uparrow), $$

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\downarrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\uparrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\downarrow) $$

* There are three states with total spin angular momentum of one

<figure><img src="image_61.png" /><figcaption>Heiter-London</figcaption></figure>

<figure><img src="image_62.png" /><figcaption>Triplet</figcaption></figure>

<figure><img src="image_63.png" /><figcaption>Ionic Form 1</figcaption></figure>

<figure><img src="image_64.png" /><figcaption>Ionic Form 2</figcaption></figure>
# Photon Upconversion

## • Clebsch-Gordan coefficients:

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\uparrow), $$

$$ \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\uparrow\downarrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, + \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\uparrow), $$

$$ \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \otimes \left| \frac{1}{2}, - \frac{1}{2} \right\rangle \quad \text{by } (\downarrow\downarrow) $$

<figure><img src="image_65.png" /></figure>

## • Triplet-triplet annihilation / Dexter electron transfer
# WDRAC: Water dimer radical-cation

The WDRACs, $(H_2O)_2^{+*}$, react with organic substances in three rather different ways:

* as electron acceptors

* as **proton donors**

* as reagents for the $OH^-$ moiety exchange

<figure><img src="image_66.png" /></figure>

WDRACs could co-exist in two different conformations:

* ion-radical structure, $H_3O^+\cdots OH^-$, with standard hydrogen bond

* two-center-three-electron non-classical **hemibonded** configuration, $(H_2O\cdots OH_2)^{+*}$

<figure><img src="image_67.png" /></figure>
# “Modern” nitrogen fixation: Haber-Bosch process

<figure><img src="image_68.png" /></figure>

* **Haber-Bosch process** (1909) is the main industrial procedure for nitrogen fixation:

$$N_2 + 3H_2 \rightarrow 2NH_3$$

* **Parameters:**

* Catalyst: Fe/FeO

* Pressure: ~200 bar

* Temperature: ~500 °C
# Ambient catalyst-free nitrogen fixation

* Ambient disproportionation reaction of N₂ with water dimer radical-cation:

$$N_2 + (H_2O)_2^{+\bullet} \rightarrow NH_2OH^{+\bullet} + HNO$$

<figure><img src="image_69.png" /></figure>
# Ambient catalyst-free nitrogen fixation

* Ambient disproportionation reaction of N₂ with water dimer radical-cation:

$$N_2 + (H_2O)_2^{+\bullet} \rightarrow NH_2OH^{+\bullet} + HNO$$

a

<figure><img src="image_70.png" /></figure>

b

<figure><img src="image_71.png" /></figure>

c

<figure><img src="image_72.png" /></figure>

d

<figure><img src="image_73.png" /></figure>

e

<figure><img src="image_74.png" /></figure>

f

<figure><img src="image_75.png" /></figure>
# Ambient catalyst-free nitrogen fixation

* Ambient disproportionation reaction of N₂ with water dimer radical cation:

$$N_2^* + (H_2O)_2^{+\bullet} \rightarrow \text{HONH-HNOH}^{+\bullet*}$$

$$\text{HONH-HNOH}^{+\bullet} \rightarrow \text{NH}_2\text{OH}^{+\bullet} + \text{HNO}$$

<figure><img src="image_76.png" /></figure>

Reaction mechanism

<figure><img src="image_77.png" /></figure>

Excited N₂ interacted with (H₂O)₂⁺
# Ambient catalyst-free nitrogen fixation

* Scaled-up setup and vibrational spectroscopy:

$$N_2^* + (H_2O)_2^{+\bullet} \rightarrow HONH-HNOH^{+\bullet*}$$

$$HONH-HNOH^{+\bullet} \rightarrow NH_2OH^{+\bullet} + HNO$$

<figure><img src="image_78.png" /></figure>

a

<figure><img src="image_79.png" /></figure>

b

<figure><img src="image_80.png" /></figure>

c

<figure><img src="image_81.png" /></figure>

d

<figure><img src="image_82.png" /></figure>

e

<figure><img src="image_83.png" /></figure>

f

<figure><img src="image_84.png" /></figure>
Part V. Above the ground(state)
# Project Parts

* **Experimental part:**

* Spectroscopic analysis of the long-lived intermediates in the process of ambient catalyst-free nitrogen fixation with water dimer

* Investigation of formic acid synthesis in CO/water plasma

* Investigation of CO₂/water & N₂O/water plasma configurations

* **Theoretical part:**

* Calculation of N₂ fixation by water radical-cations at CCSD(T) level

* Plasma parameters estimation by numerical methods

* **Industrial part:**

* Contact with hydroxylamine/nitroxyl producers

* Obtaining the grant of a patent

* Industrial project detailing
# Project Timeline

<table><thead><tr><th rowspan="2">Time</th><th colspan="3">Field</th></tr><tr><th>Experimental</th><th>Theoretical</th><th>Industrial</th></tr></thead><tbody><tr><td rowspan="4">2024</td><td>Q1</td><td rowspan="2">Building of a new plasma setup with optical profiling</td><td rowspan="2">Calculation of nitrogen fixation by water dimer radical-cation at CCSD(T) level</td><td>General market analysis</td></tr><tr><td>Q2</td><td>Gathering of leads and ideas</td></tr><tr><td>Q3</td><td rowspan="2">The new setup optimization</td><td rowspan="2">Going beyond CC-methods: application of Weizmann-1 scheme, iFCI, and MBE-FCI on (H<sub>2</sub>O)<sub>2</sub><sup>+</sup></td><td>SWOT matrix analysis</td></tr><tr><td>Q4</td><td>Contact with hydroxylamine/nitroxyl producers, wholesalers, and consumers in South Central China</td></tr><tr><td rowspan="4">2025</td><td>Q1</td><td>Investigation of methanol-plasma parameters &amp; CH<sub>3</sub>OH dimer production</td><td>Plasma parameters estimation by numerical methods</td><td>Contact with hydroxylamine/nitroxyl producers, wholesalers, and consumers in East China</td></tr><tr><td>Q2</td><td>Investigation of MTBE-plasma parameters &amp; MTBE dimer production</td><td rowspan="2">Calculation of formic acid synthesis in plasma at CCSD(T) level</td><td>Creation of a launch strategy</td></tr><tr><td>Q3</td><td>Investigation of formic acid synthesis in CO/water plasma</td><td>Initiating the process of obtaining the grant of a patent</td></tr><tr><td>Q4</td><td>Investigation of CO<sub>2</sub>/water &amp; N<sub>2</sub>O/water plasma configurations</td><td>Calculation of the long-lived intermediates in CO<sub>2</sub>/water plasma at CCSD(T) level</td><td>Getting declarations of intent (LOIs) from the potential shareholders</td></tr><tr><td rowspan="4">2026</td><td>Q1</td><td rowspan="3">Building of a new plasma reactor based on the previous findings</td><td rowspan="2">Estimation of lifetimes of dihydroxyhydrazine and its analogs by TD-DFT, CIS, and CC2 methods</td><td>Acquiring third-party funds</td></tr><tr><td>Q2</td><td>Industrial project detailing: Process engineering for nitrogen fixation by water plasma</td></tr><tr><td>Q3</td><td rowspan="2">The reactor test &amp; optimization</td><td rowspan="2">Benchmarking of recent DFT methods: SCAN, B05, and B13+ functionals</td></tr><tr><td>Q4</td><td></td></tr></tbody></table>
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References

1. Balabin, R. M., Syunyaev, R. Z., & Karpov, S. A. (2007). Molar enthalpy of vaporization of ethanol-gasoline mixtures and their colloid state. In Fuel (Vol. 86, Issue 3, pp. 323-327).

2. Syunyaev, R. Z., & Balabin, R. M. (2007). Frequency Dependence of Oil Conductivity at High Pressure. In Journal of Dispersion Science and Technology (Vol. 28, Issue 3, p. 419).

3. Balabin, R. M., Syunyaev, R. Z., & Karpov, S. A. (2007). Quantitative Measurement of Ethanol Distribution over Fractions of Ethanol-Gasoline Fuel. In Energy Fuels (Vol. 21, Issue 4, pp. 2460-2465). American Chemical Society (ACS). https://doi.org/10.1021/ef070081l

4. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2007). Comparison of linear and nonlinear calibration models based on near infrared (NIR) spectroscopy data for gasoline properties prediction. In Chemometrics and Intelligent Laboratory Systems (Vol. 88, Issue 2, pp. 183-188). https://doi.org/10.1016/j.chemolab.2007.04.006

5. Balabin, R. M., & Safieva, R. Z. (2007). Capabilities of near Infrared Spectroscopy for the Determination of Petroleum Macromolecule Content in Aromatic Solutions. In Journal of Near Infrared Spectroscopy (Vol. 15, Issue 6, pp. 343-349). SAGE. https://doi.org/10.1255/jnirs.749

6. Balabin, R. M. (2008). Dispersed Structure of Ethanol-Gasoline Fuel According to Dynamic Light Scattering Method. In Journal of Dispersion Science and Technology (Vol. 29, Issue 3, pp. 457-463). Informa UK Limited. https://doi.org/10.1080/01932690701718925

7. Balabin, R. M., & Syunyaev, R. Z. (2008). Petroleum resins adsorption onto quartz sand: Near infrared (NIR) spectroscopy study. In Journal of Colloid and Interface Science (Vol. 318, Issue 2, pp. 167-174). Elsevier BV. https://doi.org/10.1016/j.jcis.2007.10.045

8. Balabin, R. M., & Safieva, R. Z. (2008). Gasoline classification by source and type based on near infrared (NIR) spectroscopy data. In Fuel (Vol. 87, Issue 7, pp. 1096-1101).

9. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2008). Wavelet neural network (WNN) approach for calibration model building based on gasoline near infrared (NIR) spectra. In Chemometrics and Intelligent Laboratory Systems (Vol. 93, Issue 1, pp. 58-62). Elsevier BV. https://doi.org/10.1016/j.chemolab.2008.04.003

10. Balabin, R. M., & Safieva, R. Z. (2008). Motor oil classification by base stock and viscosity based on near infrared (NIR) spectroscopy data. In Fuel (Vol. 87, Issue 12, p. 2745).

11. Balabin, R. M. (2008). Intermolecular dispersion interactions of normal alkanes with rare gas atoms: van der Waals complexes of n-pentane with helium, neon, and argon. In Chemical Physics (Vol. 352, Issues 1-3, pp. 267-275). Elsevier BV. https://doi.org/10.1016/j.chemphys.2008.06.015

12. Balabin, R. M. (2008). Enthalpy difference between conformations of normal alkanes: Intramolecular basis set superposition error (BSSE) in the case of n-butane and n-hexane. In The Journal of Chemical Physics (Vol. 129, Issue 16, p. 164101). AIP Publishing. https://doi.org/10.1063/1.2997349

13. Syunyaev, R. Z., & Balabin, R. M. (2008). Polarization of Fluorescence of Asphaltene Containing Systems. In Journal of Dispersion Science Technology (Vol. 29, Issue 10, p. 1505).

14. Balabin, R. M. (2009). Enthalpy Difference between Conformations of Normal Alkanes: Raman Spectroscopy Study of n-Pentane and n-Butane. In The Journal of Physical Chemistry A (Vol. 113, Issue 6, pp. 1012-1019). American Chemical Society (ACS). https://doi.org/10.1021/jp809639s

15. Syunyaev, R. Z., Balabin, R. M., Akhatov, I. S., & Safieva, J. O. (2009). Adsorption of Petroleum Asphaltenes onto Reservoir Rock Sands Studied by Near-Infrared (NIR) Spectroscopy. In Energy Fuels (Vol. 23, Issue 3, pp. 1230-1236). ACS. https://doi.org/10.1021/ef8006068

16. Balabin, R. M. (2009). Polar (Acyclic) Isomer of Formic Acid Dimer: Gas-Phase Raman Spectroscopy Study and Thermodynamic Parameters. In The Journal of Physical Chemistry A (Vol. 113, Issue 17, pp. 4910-4918). American Chemical Society (ACS). https://doi.org/10.1021/jp9002643

17. Balabin, R. M., & Lomakina, E. I. (2009). Neural network approach to quantum-chemistry data: Accurate prediction of density functional theory energies. In The Journal of Chemical Physics (Vol. 131, Issue 7, p. 074104). AIP Publishing. https://doi.org/10.1063/1.3206326

18. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2008). Universal technique for optimization of neural network training parameters: gasoline near infrared data example. In Neural Computing and Applications (Vol. 18, Issue 6, pp. 557-565). Springer. https://doi.org/10.1007/s00521-008-0213-3

19. Balabin, R. M. (2009). Conformational equilibrium in glycine: Focal-point analysis and ab initio limit. In Chemical Physics Letters (Vol. 479, Issues 4-6, pp. 195-200).

20. Balabin, R. M. (2009). Tautomeric equilibrium and hydrogen shifts in tetrazole and triazoles: Focal-point analysis and ab initio limit. In J Chem Phys (Vol. 131, Issue 15, p. 154307).

21. Balabin, R. M., & Safieva, R. Z. (2011). Biodiesel classification by base stock type (vegetable oil) using near infrared spectroscopy data. In Analytica Chimica Acta (Vol. 689, Issue 2, pp. 190-197). https://doi.org/10.1016/j.aca.2011.01.041
References

22. Chingin, K., Balabin, R. M., Barylyuk, K., Chen, H., Frankevich, V., & Zenobi, R. (2010). Rhodamines in the gas phase: cations, neutrals, anions, and adducts with metal cations. In Physical Chemistry Chemical Physics (Vol. 12, Issue 37, p. 11710). RSC. https://doi.org/10.1039/c000807a

23. Balabin, R. M. (2010). The identification of the two missing conformers of gas-phase alanine: a jet-cooled Raman spectroscopy study. In Physical Chemistry Chemical Physics (Vol. 12, Issue 23, p. 5980). Royal Society of Chemistry (RSC). https://doi.org/10.1039/b924029b

24. Chingin, K., Balabin, R. M., Frankevich, V., Chen, H., Barylyuk, K., Nieckarz, R., Fedorov, A., & Zenobi, R. (2010). Optical properties of protonated Rhodamine 19 isomers in solution and in the gas phase. In Physical Chemistry Chemical Physics (Vol. 12, Issue 42, p. 14121). https://doi.org/10.1039/c0cp00482k

25. Barylyuk, K. V., Chingin, K., Balabin, R. M., & Zenobi, R. (2010). Fragmentation of benzylpyridinium "thermometer" ions and its effect on the accuracy of internal energy calibration. In The Journal of the American Society for Mass Spectrometry (Vol. 21, Issue 1, pp. 172-177). ACS. https://doi.org/10.1016/j.jasms.2009.09.023

26. Balabin, R. M. (2009). Conformational Equilibrium in Glycine: Experimental Jet-Cooled Raman Spectrum. In The Journal of Physical Chemistry Letters (Vol. 1, Issue 1, pp. 20-23).

27. Schmid, T., Sebesta, A., Stadler, J., Opilik, L., Balabin, R. M., & Zenobi, R. (2010). Tip-enhanced Raman spectroscopy and related techniques in studies of biological materials. In J. J. Dubowski, D. B. Geohegan, & F. Träger (Eds.), SPIE (Vol. 7586, p. 758603). https://doi.org/10.1117/12.845471

28. Chingin, K., Frankevich, V., Balabin, R. M., Barylyuk, K., Chen, H., Wang, R., & Zenobi, R. (2010). Direct Access to Isolated Biomolecules under Ambient Conditions. In Angewandte Chemie (Vol. 49, Issue 13, pp. 2358-2361). Wiley. https://doi.org/10.1002/anie.200906213

29. Balabin, R. M. (2010). Boryl Substitution of Acetaldehyde Makes It an Enol: Inconsistency between Gn/CBS and Ab Initio/DFT Data. In The Journal of Physical Chemistry A (Vol. 114, Issue 10, pp. 3698-3702). American Chemical Society (ACS). https://doi.org/10.1021/jp911802v

30. Balabin, R. M. (2010). Communications: Intramolecular basis set superposition error as a measure of basis set incompleteness: Can one reach the basis set limit without extrapolation? In The Journal of Chemical Physics (Vol. 132, Issue 21, p. 211103). AIP. https://doi.org/10.1063/1.3430647

31. Balabin, R. M. (2010). Communications: Is quantum chemical treatment of biopolymers accurate? Intramolecular basis set superposition error (BSSE). In The Journal of Chemical Physics (Vol. 132, Issue 23, p. 231101). AIP. https://doi.org/10.1063/1.3442466

32. Balabin, R. M. (2010). Reply to "Comment on 'Enthalpy Difference between Conformations of Normal Alkanes: Raman Spectroscopy Study of n-Pentane and n-Butane.'" In The Journal of Physical Chemistry A (Vol. 114, Issue 24, pp. 6729-6730). ACS. https://doi.org/10.1021/jp103852d

33. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2010). Gasoline classification using near infrared (NIR) spectroscopy data: Comparison of multivariate techniques. In Analytica Chimica Acta (Vol. 671, Issues 1-2, pp. 27-35). Elsevier BV. https://doi.org/10.1016/j.aca.2010.05.013

34. Opilik, L., Schmid, T., Stadler, J., Balabin, R. M., & Zenobi, R. (2010). Nanoscale Chemical Analysis of Cell Membrane Constituents Using Tip-Enhanced Raman Spectroscopy. In AIP Conference Proceedings (pp. 1271-1272). AIP. https://doi.org/10.1063/1.3482420

35. Amantonico, A., Urban, P. L., Fagerer, S. R., Balabin, R. M., & Zenobi, R. (2010). Single-Cell MALDI-MS as an Analytical Tool for Studying Intrapopulation Metabolic Heterogeneity. In Analytical Chemistry (Vol. 82, Issue 17, p. 7394). ACS. https://doi.org/10.1021/ac1015326

36. Zhu, L., Hu, Z., Gamez, G., Law, W. S., Chen, H., Yang, S., Chingin, K., Balabin, R. M., Wang, R., Zhang, T., & Zenobi, R. (2010). Simultaneous sampling of volatile and non-volatile analytes in beer for fast fingerprinting by extractive electrospray ionization mass spectrometry. In Analytical and Bioanalytical Chemistry (Vol. 398, Issue 1, pp. 405-413).

37. Balabin, R. M. (2010). The First Step in Glycine Solvation: The Glycine-Water Complex. In The Journal of Physical Chemistry B (Vol. 114, Issue 46, pp. 15075-15078).

38. Balabin, R. M., & Lomakina, E. I. (2011). Support vector machine regression (LS-SVM)—an alternative to artificial neural networks (ANNs) for the analysis of quantum chemistry data? In Physical Chemistry Chemical Physics (Vol. 13, Issue 24, p. 11710). RSC. https://doi.org/10.1039/c1cp00051a

39. Law, W. S., Chen, H. W., Balabin, R., Berchtold, C., Meier, L., & Zenobi, R. (2010). Rapid fingerprinting and classification of extra virgin olive oil by microjet sampling and extractive electrospray ionization mass spectrometry. In Analyst (Vol. 135, Issue 4, p. 773) https://doi.org/10.1039/b924156f
References

40. Balabin, R. M. (2011). Conformational equilibrium in alanine: Focal-point analysis and ab initio limit. In Computational and Theoretical Chemistry (Vol. 965, Issue 1, pp. 15–21).

41. Barylyuk, K., Balabin, R. M., Grünstein, D., Kikkeri, R., Frankevich, V., Seeberger, P. H., & Zenobi, R. (2011). What Happens to Hydrophobic Interactions during Transfer from the Solution to the Gas Phase? The Case of Electrospray-Based Soft Ionization Methods. In Journal of the American Society for Mass Spectrometry (Vol. 22, Issue 7, pp. 1167–1177).

42. Balabin, R. M., & Smirnov, S. V. (2011). Variable selection in near-infrared spectroscopy: Benchmarking of feature selection methods on biodiesel data. In Analytica Chimica Acta (Vol. 692, Issues 1–2, pp. 63–72). Elsevier BV. https://doi.org/10.1016/j.aca.2011.03.006

43. Balabin, R. M., Lomakina, E. I., & Safieva, R. Z. (2011). Neural network (ANN) approach to biodiesel analysis: Analysis of biodiesel density, kinematic viscosity, methanol and water contents. In Fuel (Vol. 90, Issue 5, p. 2007). https://doi.org/10.1016/j.fuel.2010.11.038

44. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2011). Near-infrared (NIR) spectroscopy for motor oil classification: From discriminant analysis to support vector machines. In Microchemical Journal (Vol. 98, Issue 1, pp. 121–128). Elsevier BV. https://doi.org/10.1016/j.microc.2010.12.007

45. Balabin, R. M., & Safieva, R. Z. (2011). Near-Infrared (NIR) Spectroscopy for Biodiesel Analysis: Fractional Composition, Iodine Value, and Cold Filter Plugging Point from One Vibrational Spectrum. In Energy Fuels (Vol. 25, Issue 5, pp. 2373–2382). ACS. https://doi.org/10.1021/ef200356h

46. Balabin, R. M., & Smirnov, S. V. (2011). Melamine detection by mid- and near-infrared (MIR/NIR) spectroscopy: A quick and sensitive method for dairy products analysis. In Talanta (Vol. 85, Issue 1, p. 562). https://doi.org/10.1016/j.talanta.2011.04.026

47. Chingin, K., Balabin, R. M., Frankevich, V., Barylyuk, K., Nieckarz, R., Sagulenko, P., & Zenobi, R. (2011). Absorption of the green fluorescent protein chromophore anion in the gas phase studied by a combination of FTICR mass spectrometry with laser-induced photodissociation spectroscopy. In International Journal of Mass Spectrometry (Vol. 306, Issues 2–3, pp. 241–245). Elsevier BV. https://doi.org/10.1016/j.ijms.2011.01.014

48. Likhatsky, V. V., Balabin, R. M., & Syunyaev, R. Z. (2011). Calculation of Dipole Moment of Fractal Asphaltene Cluster. In Journal of Dispersion Science and Technology (Vol. 32, Issue 10, pp. 1502–1508). Informa UK Limited. https://doi.org/10.1080/01932691.2010.516129

49. Balabin, R. M., & Lomakina, E. I. (2011). Support vector machine regression (SVR/LS-SVM)—an alternative to neural networks (ANN) for analytical chemistry? Comparison of nonlinear methods on near infrared (NIR) spectroscopy data. In The Analyst (Vol. 136, Issue 8, p. 1703). Royal Society of Chemistry (RSC). https://doi.org/10.1039/c0an00387e

50. Balabin, R. M., Syunyaev, R. Z., Schmid, T., Stadler, J., Lomakina, E. I., & Zenobi, R. (2010). Asphaltene Adsorption onto an Iron Surface: Combined Near-Infrared (NIR), Raman, and AFM Study of the Kinetics, Thermodynamics, and Layer Structure. In Energy Fuels (Vol. 25, Issue 1, pp. 189–196).

51. Balabin, R. M. (2011). On the relation between basis set convergence and electron correlation: a critical test for modern ab initio quantum chemistry on a “mindless” data set. In Structural Chemistry (Vol. 22, Issue 5, pp. 1047–1051). Springer. https://doi.org/10.1007/s11224-011-9793-0

52. Zenobi, R., Schmid, T., Syunyaev, R. Z., & Balabin, R. M. (2011). Physical chemistry of acridine adsorption onto gold surface: the influence of nanostructure as revealed by near-infrared and tip-enhanced Raman spectroscopy (TERS). In Physical Chemistry of Interfaces and Nanomaterials X (p. 25). Physical Chemistry of Interfaces and Nanomaterials X.

53. Balabin, R. M. (2011). The keto-enol equilibrium in substituted acetaldehydes: focal-point analysis and ab initio limit. In Molecular Physics (Vol. 109, Issue 19, pp. 2341–2351).

54. Balabin, R. M., & Smirnov, S. V. (2012). Interpolation and extrapolation problems of multivariate regression in analytical chemistry: benchmarking the robustness on near-infrared (NIR) spectroscopy data. In The Analyst (Vol. 137, Issue 7, p. 1604). RSC. https://doi.org/10.1039/c2an15972d

55. Barylyuk, K., Fritsche, L., Balabin, R. M., Nieckarz, R., & Zenobi, R. (2012). Gas-phase basicity of several common MALDI matrices measured by a simple experimental approach. In RSC Advances (Vol. 2, Issue 5, p. 1962). Royal Society of Chemistry (RSC). https://doi.org/10.1039/c1ra01117k

56. Balabin, R. M. (2012). Experimental thermodynamics of free glycine conformations: the first Raman experiment after twenty years of calculations. In Phys. Chem. Chem. Phys. (Vol. 14, Issue 1, pp. 99–103). Royal Society of Chemistry (RSC). https://doi.org/10.1039/c1cp20805e

57. Balabin, R. M. (2011). Enthalpy difference between conformations of normal alkanes: effects of basis set and chain length on intramolecular basis set superposition error. In Molecular Physics (Vol. 109, Issue 6, pp. 943–953). Informa UK Limited. https://doi.org/10.1080/00268976.2011.558858
58. Barylyuk, K., Balabin, R. M., Grünstein, D., Kikkeri, R., Frankevich, V., Seeberger, P. H., & Zenobi, R. (2011). What Happens to Hydrophobic Interactions during Transfer from the Solution to the Gas Phase? The Case of Electrospray-Based Soft Ionization Methods. In Journal of the American Society for Mass Spectrometry (Vol. 22, Issue 7, pp. 1167–1177).

59. Balabin, R. M., & Smirnov, S. V. (2011). Variable selection in near-infrared spectroscopy: Benchmarking of feature selection methods on biodiesel data. In Analytica Chimica Acta (Vol. 692, Issues 1–2, pp. 63–72). Elsevier BV. https://doi.org/10.1016/j.aca.2011.03.006

60. Balabin, R. M., Lomakina, E. I., & Safieva, R. Z. (2011). Neural network (ANN) approach to biodiesel analysis: Analysis of biodiesel density, kinematic viscosity, methanol and water contents. In Fuel (Vol. 90, Issue 5, p. 2007). Elsevier BV. https://doi.org/10.1016/j.fuel.2010.11.038

61. Balabin, R. M., Safieva, R. Z., & Lomakina, E. I. (2011). Near-infrared (NIR) spectroscopy for motor oil classification: From discriminant analysis to support vector machines. In Microchemical Journal (Vol. 98, Issue 1, pp. 121–128). Elsevier BV. https://doi.org/10.1016/j.microc.2010.12.007

62. Balabin, R. M., & Safieva, R. Z. (2011). Near-Infrared (NIR) Spectroscopy for Biodiesel Analysis: Fractional Composition, Iodine Value, and Cold Filter Plugging Point from One Vibrational Spectrum. In Energy Fuels (Vol. 25, Issue 5, pp. 2373–2382). ACS. https://doi.org/10.1021/ef200356h

63. Balabin, R. M., & Smirnov, S. V. (2011). Melamine detection by mid- and near-infrared (MIR/NIR) spectroscopy: A quick and sensitive method for dairy products analysis. In Talanta (Vol. 85, Issue 1, p. 562). Elsevier BV. https://doi.org/10.1016/j.talanta.2011.04.026

64. Chingin, K., Balabin, R. M., Frankevich, V., Barylyuk, K., Nieckarz, R., Sagulenko, P., & Zenobi, R. (2011). Absorption of the green fluorescent protein chromophore anion in the gas phase studied by a combination of FTICR mass spectrometry with laser-induced photodissociation spectroscopy. In International Journal of Mass Spectrometry (Vol. 306, Issues 2–3, pp. 241–245). Elsevier BV. https://doi.org/10.1016/j.ijms.2011.01.014

65. Zhang, X., Su, R., Li, J., Huang, L., Yang, W., Chingin, K., Balabin, R., Wang, J., Zhang, X., Zhu, W., Huang, K., Feng, S., & Chen, H. (2024). Efficient catalyst-free N2 fixation by water radical cations under ambient conditions. Nature Communications.

66. Zhang, X., Hu, P., Duan, M., Chingin, K., Balabin, R., Zhang, X., & Chen, H. (2024). Ambient catalyst-free oxidation reactions of aromatic amines using water radical cations.

67. Balabin, R. V., Volkomirskaya, L. B., Gulevich, O. A., Krivosheev, N. V., Lyakhov, G. A., Musalev, D. N., Reznikov, A. E., Safieva, R. Z., & Semyonov, S. N. (2015). Georadar sensing from terrestrial surface and shafts: Approaches to evaluation of rock fracturing. In Physics of Wave Phenomena, 23 (2), 143–153. https://doi.org/10.3103/s1541308x15020107

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