PB 161632

^ecUniccil vtote 131

PHOTOIONIZATION OF ATOMS

AND MOLECULES

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
THE NATIONAL BUREAU OF STANDARDS

Functions and Activities *

The functions of the National Bureau of Standards are set forth in the Act of Congress, March 3, 1901, as amended by Congress in Public Law 619, 1950. These include the development and maintenance of the national standards of measurement and the provision of means and methods for making measurements consistent

with these standards; the determination of physical constants and properties of materials; the development of methods and instrimients for testing materials,- devices, and structures; advisory services to government agencies on scientific and technical problems; invention and development of devices to serve special needs of the Government; and the development of standard practices, codes, and specifications. The work includes basic

and applied research, development, engineering, instrumentation, testing, evaluation, calibration services,

and various consultation and information services. Research projects are also performed for other government

agencies when the work relates to and supplements the basic program of the Bureau or when the Bureau's

unique competence is required. The scope of activities is suggested by the listing of divisions and sections on the inside of the back cover.

Publications

The results of the Bureau's research are published either in the Bureau's own series of publications or

in the journals of professional and scientific societies. The Bureau itself publishes three periodicals avail- able from the Government Printing Office: The Journal of Research, published in four separate sections,

presents complete scientific and technical papers; the Technical News Bulletin presents summary and pre- liminary reports on work in progress; and Basic Radio Propagation Predictions provides data for determining

the best frequencies to use for radio communications throughout the world. There are also five series of nonperiodical publications: Monographs, Applied Mathematics Series, Handbooks, Miscellaneous Publications,

and Technical Notes. A complete listing of the Bureau's publications can be found in National Bureau of Standards Circular

460, Publications of the National Bureau of Standards, 1901 to June 1947 ($1.25), and the Supplement to National Bureau of Standards Circular 460, July 1947 to June 1957 ($1.50), and Miscellaneous Publication 240,

July 1957 to June 1960 (Includes Titles of Papers Published in Outside Journals 1950 to 1959) ($2.25); avail- able from the Superintendent of Documents, Government Printing Office, Washington 25, D. C.
NATIONAL BUREAU OF STANDARDS

technical Niote

131

JANUARY 1962

PHOTOIONiZATION OF ATOMS

AND MOLECULES

Fred L. Mohler

NBS Technical Notes are designed to supplement the Bureau's regular publications program. They provide a means for making available scientific data that are of transient or limited interest. Technical Notes may be

listed or referred to in the open literature. They are for sale by the Office of Technical Services, U. S. Department of Commerce, Washington 25, D. C.

DISTRIBUTED BY

UNITED STATES DEPARTMENT OF COMMERCE

OFFICE OF TECHNICAL SERVICES

WASHINGTON 25, D. C.

Price $1.25
TABLE OF CONTENTS

PAGE

ABSTRACT 1

1. INTRODUCTION 1

2. EXPERIMENTAL METHODS 3

3. EXPERIMENTAL RESULTS 5

3.1. Forword 5

3.2. Photolonlzatlon Cross Sections

of Atoms 6

3.3. Photolonlzatlon Cross Sections

of Some Molecules 10

4. SUMMARY 16

5. REFERENCES 17

II
Photolonlzatlon of Atoms and Molecules

by Fred L. Mohler*

This Is a review of experimental results on photolonlzatlon of atoms and some molecules. There are some quantitative data on all the alkalies^ magnesium^ calcium

and thallium and all rare gases except xenon. Results

are given for the common gases; hydrogen, nitrogen, oxygen,

CO, CO2, NO, N2O, NO2, H2O and CH4. Auto Ionization, excitation to a state above the ionization threshold followed

by transltloh to the Ionized state, can be an important

factor. Often the broad autolonlzation lines mask the true

continuum. There are some mass spectrometric measurements

of photolonlzatlon products for most of these molecules.

1. INTRODUCTION

The purpose of this report is to give a survey and bibliography

of experimental measurements of photolonlzatlon and of the continuous

absorption bands resulting In photolonlzatlon. The scope of this

report will include atoms and some simple diatomic and polyatomic

molecules. A survey of this subject through 1955 is given in a Handbuch der Physik article by G. L. Welssler [l].

Ever since the publication of Bbhr's theory of atomic structure

it. has been recognized that beyond each absorption series there will

be a continuous absorption band ari.sing from removal of an electron

from the atom with kinetic energy. Characteristic X-ray absorption

spectra are photolonlzatlon contlnua that have been quite systematically studied [2]. The absorption for each X-ray level begins abruptly

at the series limit and decreases roughly as the cube of the wavelength

X. A general formula for this absorption is

"^n - <:, ^ J^" n n where cr^ 's the atomic absorption coefficient for each X-ray level K,

Lj, L2f L3, M], M2, etc., and Cn I s a constant Involving the quantum

numbers of each X-ray level and the threshold wavelength of the level

and Z is the atomic number, a is roughly h and b ranges from 2.5 to 3.

^Consultant to the Atomic Physics Division, NBS.

-1-
In contrast to the X-ray range, the experimental data on photoionization of valence electrons remain to this day quite fragmentary

and incomplete. The photoionization bands fall in general in the

vacuum ultraviolet which involves serious experimental difficulties.

Furthermore, there are relatively few elements that are monatomic in

the gas phase. The rare gases are the only elements that are purely

monatomic. Vapors of the electro-positive metals are predominantly

monatomic, but in most cases diatomic molecules of relatively low

stability have also been observed In the vapor [3].

The photoionization absorption is conveniently e;q>ressed in terms

of the absorption per atom (the effective atomic collision area for

the photon) here written as a. It is also e^ressed as the absorption

per cm, a, in gas at normal pressure and temperature,

CT - a X 3.72 X

10"^°.

One can measure the absorption of a column of gas at a icnown

pressure, or alternatively one can measure the ion current produced

by a measured radiation flux LS,$1 In gas at a known pressure. This

alternative method can be used in metal vapors at pressures too low to

give measurable absorption.

in most atoms there are excited states of the neutral atom which

fall above the first ionization threshold, and these states can pass

spontaneously , into the ionized state. Excitation of these states

gives absorption lines which are commonly unsymmetrical ly broadened

on the short wavelength side and the widths indicate half lives ranging

down to 10" '5 sec or less. These lines have not been observed In

emission and presumably radiation transitions are negligible compared

with autolonlzation [4j. Autoionlzatlon in some cases maizes contributions to the total photoionization that are large compared with the

continuous absorption. In the extreme ultraviolet, line emission sources

are commonly used and line sources cannot give quantitative Information

on line absorption processes, although fortuitously the line spectra

often overlap the broad absorption lines.

There are some instances of photoionization produced in a two step

process by line absorption below the first ionization potential. Thus

Foote and Mohler [7] found that there is some ionization by line

absorption in cesium vapor. The efficiency of ionization Is proportional

to the pressure, and It can be explained by the assumption that highly

excited atoms react with neutral atoms to form molecule Ions [8]. This

and other similar pressure dependent reactions will not be included in

this survey.

-2-
In the photoloni zation of molecules the number of Ions produced

may be less than the number of quanta absorbed and the ratio (here

expressed In percent) Is called the efficiency of photoloni zation.

Commonly the efficiency is low near the threshold.

In the Ionization of molecules the products can be either molecule

Ions or fragment Ions, and it requires a mass spectrometric analysis to

obtain a complete Interpretation of the results. In practice it Is best

to measure the ionization cross section In a simple ionization chamber

and use the mass spectrometric measurement to evaluate relative abundances of different Ions.

.2. EXPERIMENTAL METHODS

The rare gases are purely monatomic and a direct measurement of the

continuous absorption affords the simplest method of evaluating the

atomic cross section for photoloni zation. There is the complication

that the continuous spectra fall in the extreme ultraviolet and nearly

all window materials are opaque to this radiation. Effective sources

for the far ultraviolet are intense discharges In hydrogen, helium or argon, or high vacuum sparks between metal electrodes. In any case, it

is essential to separate the discharge region and the gas being studied.

Weissler and his colleagues [l] have used a differential pumping chamber

between the source and the spectrometer entrance slit. DItchburn [36]

has found It feasible to use thin sheets of collodion over the silt to

separate the discharge and the gas being studied.

High temperatures and chemical reaction with windows are a difficulty in measurements with most of the metal vapors. DItchburn and

his associates Cl6] have used a tube of the following design to keep

windows cool and clear. The metal vapor is confined by two metal plugs

to the central half of a nickel tube about 2 meters long. These plugs are about 10 cm long with holes 6 mm in diameter along the axis. The

mid-sectlon is held at a temperature which gives a convenient vapor

pressure, the plugs are at a slightly higher temperature, and the rest

of the tube Is cool. Helium at roughly 1 cm pressure Is in the tube,

and this slows up the diffusion of the metal and keeps It from reaching

the windows. The experimental uncertainty in the vapor pressure, temperature data is probably the major source of uncertainty.

Intensity measurements can be made either by a photomul tipl ier or

by photographic densitometry. Electrical measurements can give better

precision, but photographs give optimum resolving power which Is Important when autoioni zation peaks are present. In measurements at wavelengths of less than lOOOA, sources giving line emission spectra are

commonly used and autioni zation cannot be measured quantitatively.

-3-
Measurements of photolonizatlon cross sections can be niade by

passing a beam of radiation through a simple parallel plate ionization

chamber In gas at a measured pressure. The beam strikes a thermopile

or the sensitized surface of a photomul tipl ler bulb which measures the

photon flux [5]. A surface of sodium salicylate gives a nearly constant

quantum sensitivity in the range (to about lOOOA) in which it Is

feasible to calibrate It with a thermopile. Welssler's group have used

two or three Ionization chambers spaced along a tube containing the

gas to measure both the absorption and the photolonlzatlon [6].

In pioneer studies of photolonlzatlon of cesium vapor, Foote and

Mohler [7] used the space charge effect of positive ions on thermionic

emission from a hairpin cathode to detect photolonlzatlon. When the

voltage in a diode Is reduced to one or two volts the current is limited

by space charge and there Is a potential minimum In the region around

the filament. If positive Ions are produced In this region, they are

trapped and neutralize the space charge. One Ion can liberate more

than 10^ electrons and this large amplification factor made it simple

to measure photolonlzatlon as a function of wavelength. Absolute

measurements were made at a few wavelengths with a simple ionization

chamber and measured radiation flux [19].

Mass spectrometrlc research on photolonlzatlon of molecules Is

with one notable exception a relatively new field of research. In

1932 Terenin and Popov [9] found that thallium iodide, bromide and

chloride are Ionized by radiation transmitted by a quartz mohochromator,

A simple magnetic spectrometer showed that the ions are Tl"*" and l' or Br" for the iodide or bromide. The Ion current reached a peak value

near 2125A for Tl 1 and 2000A for Tl Br. The cross section for photolonlzatlon was of the order of 10"' 7 cm^.

In recent years Hurzeler, Inghram, and Morrison [lO] have used a mass spectrometer to study ionization products produced by resolved

ultraviolet radiation transmitted by a lithium fluoride window. They

reported on a variety of organic molecules which are ionized by

radiation of wavelength greater than IO8OA. Weissler, Samson, Ogawa

and Cook [46] measured mass spectra of photolonlzatlon products without

a window between the monochromator and the Ionization chamber, and preliminary results have been published for 02^ N2, CO, NO, C02> N2O and

NO2.

-4-
Lassettre and his staff at Ohio State University have made careful

measurements of the probability of Inelastic scattering of 500 ev electrons as a function of the energy lost In collision. Studies Include

helium, nitrogen, oxygen, carbon monoxide, carbon dioxide and water [I3].

He assumes with supporting evidence that at 500 ev the Born approximation

is valid and probabilities of Inelastic collision can be related to

probabilities of photon absorption. This affords an alternative method

of deriving photolonlzatlon cross sections that avoids the difficulties

of far ultraviolet research. Results seem to be consistent with optical

measurements, but resolving power Is less and except In helium transitions

to discrete states tend to mask the contlnua.

3. EXPERIMENTAL RESULTS

3.1. Foreword

The following summary of experimental results gives photolonlzatlon

cross sections for atoms and some molecules. The section on molecules

Is limited to common diatomic molecules and simple polyatomic molecules,

with particular attention to molecules that might be found In the upper

air. Wi th a few exceptions, the list is limited to researches affording

a quantitative basis for estimating atomic or molecular cross sections

for photolonlzatlon.

For each atom, following the ch&i\\ca] symbol for the element, the

Ionization threshold is given in angstrom units and In electron volts.

The configuration Is given for the normal state or for the Ionized

states in customary spectral notation. Data are taken from Charlotte

Moore' s "Circular on Atomic Energy Levels" [ll]. The elements are

arranged according to columns of -the periodic table beginning with

hydrogen and the alkalies.

For molecules spectral notation of the normal state is not given.

The threshold Is commonly the first of a group of "Rydberg series limits"

and some Information on the other limits Is given.

Figures showing atomic or molecular cross sections as a function

of wavelength or electron volts are given for nearly all the atoms and

molecules. These are all taken from the sources indicated without

editing and a variety of coordinates are used. In this field a common

unit of cross section Is the "megabarn", Mb, which Is 10"^° cm2.

-5-
3.2. Photoiontzation Cross Sections of Atcsms

H X « 912A 13.595 ev Normal state Is^S, ,0 o 1/2

There are no experimental measurements of C7^ but the theory Is

reliable and gives as a good approximation [14]

o - 6.33 X lo"'^ (XAq)^

Li X = 23OOA 5.390 ev Normal state 2s ^S, ,«. o i/2

Tunstead [I5] measured the absorption cross section in the range

23OOA to 1800A. CTq (23OOA) is 2.5 ± .5 X 10"^° cm^ a decreases with

decreasing wavelength, and c (1800/\) is 1.35 x 10"'". It decreases in

this range as X^*^. See figure 1.

Na^ Xq » 241 2A 5.138 ev Normal state 3s ^S^ ,,

Ditchburn, et al., [16] measured the absorption cross section in

the range 2412 to 1600A, and Hudson [I7] has extended the measurements

to llOOA.

CTq (2412^= .116 ± .012 X 10"'8 cm2 and drops sharply to .013 x lO'lS

at I95OA and rises to a sharp maximum a = .4 x 10"'° at 1400A, and Is

less than .01 x 10"'8 at 1 lOOA. See figure 2. A correction for molecular

absorption has been made [16] by measuring absorption as a function of

pressure and extrapolating to low pressure.

K Xq = 2856A 4.339 ev Normal state 4s ^S^ .^

DItchburn, Tunstead and Yates [I8] measured the absorption

coefficient to I6OOA and measurements at different pressures gave a correction for some molecular absorption,

cTq (2856A) = .012 ± .003 X

10"^^ cm2 and drops to .008 x

10"'^

at 27OOA, and rises to .24 x 10"l8 at I6OOA. See figure 3.

Photolonizatlon measurements confirm the shape of the absorption

curve to 2200A [19,20].

K- amounts to less than 3 percent of the vapor at the highest vapor

pressures and the absorption is negligible to 2100A but o (K2) rises to

roughly 10 x lO"^^ gt I70OA [22].

Rb Xq " 2968a 4.176 ev Normal state 5s ^S, ^^

-6-
Wohler and Boeckner [19] measured photoionlzatlon^ln the range

2968a to 23OOA. They used the spac6 charge effect combined with a measurement in a simple ionization chamber with radiation of measured

quantum flux.

CTq (2968a) » 0.11 X 10" '8 cm^. a drops rapidly with decreasing X

reaching nearly at 2550A and remains low to 2300A. See figure k,

Beutler [21] has observed 39 absorption lines in the range 81 OA to

594a which presumably give autoionization. They fall in series that

converge to 3p and 'P limits of the configuration %)5 5s.

Cs \ » 3184a 3.893 ev Normal state 6s ^S, ,^ O 1/2

Braddick and Oltchburn [22] measured the absorption from 3184A to

23OOA.

cTq (3184a) « .22 ± .01 X

10"'^ cm^ and drops to .O78 x 10''^ near 28OOA and rises to .15 x 10"'° near 2^0A. See figure 5. The absorption

is proportional to the pressure. Mohler and Boeckner [I9] measured the

photoionization in this range. T^fir values are cTq = .23 ± .02 x 10"'|.

a reaches a minimum of .043 x 10"'° near 2600A and rises to .08 x 10"'°

near 2200A. Beutler and Guggenhelmer [23] find absorption lines beginning

at 999A which converg to ^P and "p limits 721A, 719A, 65IA and 649A of

the configuration 5p 6s.

2

Mg X = 1610A 7.64 ev Ionized state 3s S

* o DItchburn and Marr [24] have measured absorption from 1610A to 1450A.

Cq (161 OA) Is 1.18 ± .25 X 10" '8 an2 and a decreases sharply to 0.2 x

10"'° at I45OA. The absorption is directly proportional to the pressure.

See figure 6.

2

Ca \ » 2028A 6.11 ev Ionized state 4s S o

\jj = 1589A 7.82 ev Ionized state 3d V^^

3/2

Jutsum [26] and DItchburn and Hudson [25] have measured absorption In

the range 2028A to llOOA. This is characterized by continuous absorption beyond 2028A and 1589A and by two series of absorption lines, much

broadened by autoionization In the range 1900A to I589A. The absorption series involve double excitation of the two valence electrons into

a 3d level and Into p levels. For the continuum a^ (2028A) = .45 ±

.07 X 10"'° cm^ and this drops sharply to zero near 1950. In the range

I9OOA to I589A it rises to about 0.45 x 10"'^ but this range is partly

masked by line absorption. At I589A it rises to 0.9 x 10"'^ and falls

to a flat minimum of .32 x 10"'^ pear 1250A and is .55 x 10"'^ at llOOA.

-7-
The first autolonlzatlon lines of the singlet P series have peak

absorption coefficients of 30 x 10~l8 and 70 x 10"'° and half-widths of

615 cm"' and 69 cm"'. See figures 7 and 8.

In \q = 2143A 5.785 ev Normal state 5s^ 5p ^P,/-

Garton [29] has published a qualitative description of the absorption

from 2143A to l^OA. Absorption decreases from 2 1^3A to nearly zero at

1800A and five intense diffuse absorption lines at 1757.3A, 17^.9A,

171 1.1 A, 1676,2A and 1648.7A dominate in |p*-«nsity. These lines come

from the configuration 5s 5p^. Marr [30] has measured the maximum atomic

absorption coefficient of the 1757A line as about 10~'° cm^ and estimates

the continuous absorption coefficient o^ (2143A) to be one percent or less of this or of the order of 10"'°.

2fl X = 203OA 6.106 ev Normal state 6s

12

6p Pwo O 1/2

Marr [27] has measured the absorption in the range 203OA to \k5Ok. Very

intense wide autolonlzatlon lines tend to mask the continuum [28],

a (203OA) = 4.5 X 10"' 8 an2. a drops to 2.1 x 10-'8 at 201 OA. ^t

I95OA It Is 4.8 X 10-18 and drops to 0.7 x 10"' 8 at 1750A. Thre, autolonlzatlon peaks are

i X o max.

2007 12 X lO'^^

1610 150 X

10"'^

1490 30 X

10"^^

2 These come from the configuration 6s 6p . The "f number" for the con- tinuum is 0.025. See figure 9.

He X « 504. 3A 24.58 ev Ionized state Is ''"S o Lee and Weissler [3I] measured the absorption in the range 504A to

240A. Axel rod and GIvens [32] extended the measurements to I5OA.

Dershem and Schein [33] In 1931 measured the absorption coefficient of

K a of carbon (X = 44. 6A) in He,

Lee and Weissler [3I] find a^ at 504A = 7.1 ± .7 x 10"'8 cm^.

a (400A) = 4,0 x 10"' 8, a (300A) » 1.66 x

10"' 8, a (240A) = .92 x

10'' 8.

Axel rod and GIvens [32] find somewhat larger values at the shorter waveths. a (3OOA) = 2.3 X 10"' 8, a (250A) = 1.6 x

10"' 8, a (2OOA) =

f number hal f width half 1 If6 Term

.005 300 cm"' 18 ± 5 X 10"Uc V/2

.52 ± .09 2450 cm"' 2,2 X 10 '^sec ^D

.005 2p

length,. ^ , . ._ , »-- , ._ .. . , ^ , .95 X 10"' 8, a (I7OA) = .73 x 10" '8 cm^. 5ee figure 10. Dershem and

Schein [33] find a (44. 6A) = 0.0238 x 10" '8 cm^

-8-
Between 504A and 200A. cr decreases as \^*'°. Between 200A and

kk,6A, o decreases as X^*^.

Wheeler [34] has computed the theoretical value as a^ « 7.4 x 10"'^.

Ne X^ - 576. 7A 21.56 ev ionized state 2s^ 2p^ ^P. ,, o

"^ 3/2

574.9A Ionized state P,/2

256A 48.5 ev Ionized state 2s 2p^ ^S

Lee and Welssler [35] and Dl tchburn [36] have measured the absorption

to 240A and 200A respectively. Data are consistent within the cange of

experimental uncertainty. Dl tchburn gives cr^ (577A) » 4 x

10'^° cm^

and a rises to a flat maximum of 8 x 10"'° near 400A and falls to

5 x '0"j8 near 256A and Jumps to 7.5 x 10"'° at 256A and falls to

5 x

10"'° near 200A. See figure 11,

Dershem and Schein [33^ ^'ncl for the absorption coefficient of

carbon K a (44. 6A) a » 0.436 x 10" '8 cm2. From 256A to 44. 6A o decreases

as X'«6.

Ar Xq = 786. 7A 15.75 ev Ionized state 3s^ 3p^ ^P3/2

777. 96A 15.91 ev Ionized state ^^]/2

6 2

424A 29.3 ev Ionized state 3s 3p S

Po Lee and Welssler [35] measured the absorption In the range 787A

to 36OA. There Is auto Ionization by absorption lines between 786. 7A and

778A [37]. There are also autolonlzatlon peaks In the range 535A to

428A^ but measurements are not quantitative as a line emission source

was used In this range.

The continuous absorption measurements give Oq (778A) = 36 x 10"'^

cm^. This Is nearly constant to 700A and drops smoothly to 14 x 10"'°

near 424a. It jumps to 19 x 10"'° at 424A and falls smoothly to 8 x

10"'°

at 36OA. See figure 12,

Walnfan, Walker and Welssler [38] measured photolonlzatlon in the

range 787A to 5OOA with values consistent with the absorption measurements,

Kr Xq « 885A 13.996 ev Ionized state 4s^ 4p^ ^P. ,«

845A 14.66 ev Ionized state ^1/2

326A 38.5 ev Ionized state 4s 4p^ ^S

-9-
Anne Pery-Thorne and Carton [39] have measured absorption *n the

range 885A to 500A. The continuum mubs measured by photomul tlpller and

the line absorption by photographic densitometry.

Between 885A and 845A the continuum is partially masked by broad

lines [^] converging at ^P]/2»

Oq (885A) Is about 30 x lO'^^ ^m^ and cr^ (845A) i s 37 ± 7 x I0"'8.

c remains nearly constant to 6OOA and drops to 30 x 10"'8 at 5OOA. See

figure 13. They measured the Integral of the absorption across each

line for doublets between 881 A and 85IA. The f numbers for the first

two doublets-are: 88IA, f = 0.0^31; 869. 5A, f =a0235; 862. 7A, f »

0.0143; 858. 5A, f - 0.0086.

3.3. Photolonl^atlon Cross Section of Some Molecules

H, \ = 804. I 3A [43] 15.42 ev

2 o Lee and Welssler [41] measured the continuous absorption In the

range 8OOA to 300A^ and found autolonlzatlon bands superposed on the

continuum In the range 770A to 67OA. Beutler and Junger [43] have

described the band system giving rise to autoionization. The rotational

fine structure of this band system suddenly become diffuse beyond 804. 13A.

The continuum rises abruptly from 804A to a value of ct = 7.4 x 10~18

cm2 near Z50A, and drops gradually to 4 x 10''^ at 400A and less than

.7 X 10"18 at 300A. See figure 14.

Walnfan, Walker and Welssler [38] measured photolonization cross section and photolonization efficiency from 800A to 65OA. The efficiency

is nearly 100 percent and the rnaximum value of cTj = 8.3 x 10"'° cm^.

Values for the bands are not quantitative^ as a line source was used.

Schonheit [42] has published a note on the mass spectrum of the

photolonization products. At 637A (19.5 ev) the relative abundance of

ions was: H,* is 1.00; H''' is 0.10; H^"*" (from collisions of H2''" and H2)

Is 0.03. The appearance potential ot H"*" 1 s I8.O5 ev [4^].

N2 Xq = 795. 74A 15.503 ev [47]

\q belongs to a group of Rydberg series limits at 796A, 742A, 66IA and

526A. Band systems converging at levels beyond 796A, give autoionization

peaks superposed on the conblnuum [47]. Measurements of autoionization

are not quantitative.

Welssler, Po Lee and Mohr [44] measured absorption In the range

796A to 3OOA, and Curtis [45] measured absorption to I5OA.

-10-
Wainfan^ Walker and Welssler [38] measured photolonization in the

range 796A to 500A and found nearly 100 percent efficiency beyond 750A.

Weissler, Samson, Ogawa and Cook [46] measured tiie mass spectrum of

tlie ions produced by photolonization for wavelengths down to 400A.

Welssler, et al., 1^2 find the continuum rises abruptly from the

threshold to a = 25 x 10''° near 750A. o Is about 22 x lO'^o at 67OA

and 27 x 10"'® near 66OA and falls almost linearly to about .7 x 10"18

at 3OOA. See figure I5. Curtis [45] finds^a similar curve but gives

absolute values about half the values reported by others. Mass spectra

show that N+ appears at 51 OA (24.3 ev) and from 480A to 400A the abundance is nearly constant and about one percent of N2'*'. The threshold

for N* Is consistent with appearance potential measurements [48].

O2 Xj^ = 1026.5A 12.09 ev

Rydberg series converge to limits 1026. 5A, 770A, 729A, 681A and 61 lA

[47]. Autolonization peaks occur in this range.

Welssler and Po Lee [49] and Po Lee [50] have measured absorption

in the range I3OOA to 200A.

Watanabe and Marmo [5I] measured photolonization and absorption

in the range 1026A to 85OA using a continuous emissiorh source.

Wainfan, Walker and Weissler [38] measured photolonization cross sections to 473A, and Weissler, Samson, Ogawa and Cook [46] measured

the mass spectrum.

Po Lee [50] used relatively high resolution. In the range 1026A

to 675A autolonization peaks partially mask the true continuum. The

continuum rises from the threshold to a value of a = 2.0 x 10"'^ cm^

at 97OA, 4.0 X 10"18 at 920A, and 3.0 x 10-18 at 85OA. From 85OA to

74OA it is masked by autolonization bands, but rises to about 20 x 10~l8

at 74OA and remains about this value to 5OOA and drops to 12 x 10"J8

near 200A. See figure 16.

Watanabe and Marmo [51 ] measured the efficiency of Ionization from

IO26A to 85OA. It ranges from 50 percent to 100 percent, and the more

Intense autolonization bands are about 5 times as strong as the background continuum. Values of cr for the continuum are consistent with

Po Lee's values. Photolonization measurements in the far ultraviolet

[38] give a nearly constant value of c; = 25 x 10"'^ cpi^ in the range

7OOA to 473A. This Is In fair agreement with Po Lee's absorption

measurements {p = 20 x 10" '8),

-11-
The mass spectrum [46] shows that 0"*" appears at 662A (18.8 ev) and

rises to a peak near 63OA. A second nearly equal peak begins at 603A

(20.7 ev) . There is some evidence of a third increase near 530A, (23.4

ev) . The three critical potentials could give the products 0+ ( S) +

(3p), 0+ (^S) + (Id) and 0+ (^S) +0 (^ S) at 18.7 ev, 20.7 ev and

22.9 ev. 0'*' currents are roughly 10 percent of the 02"*" currents and

make a relatively small contribution to the total absorption. The Do

curve gives a series of six sharp peaks, probably from autoioni zatlon,

that conceal the continuum found by Po Lee using higher resolving power.

CO X = 884.7A 13.94 ev [53] o

53].

Three Rydberg series limits are at 884. 7A, 749. 7A, and 630.2A [52,

Sun and Welssler [55] measured the absorption In the range 885A

to 374A.

Watanabe [54] measured the photolonizatlon near the threshold.

Welssler, Samson, Ogawa and Cook [46] measured photolonizatlon

wl th a mass spectrometer to 400A.

Photolonizatlon begins with a steep Increase at the threshold

884. 7A. The continuum, partially masked by autolonl zation peaks, has

a broad flat maximum near 500A of a = 18 x 10"'° cm^. It Is 15 x lO"'^

or more from 7OOA to AOOA, and 13 x 10"^^ cm^ at 374A. See figure 17.

C"*" appears near 596A (20.8 ev) . It remains less than one percent

of CO"'" to 556A (22.3 ev) and then Increases to two percent of CO"*". There Is some evidence of increases at 24.8 ev and 26.4 ev. These

critical potentials have also been observed in electron Impact studies

[48] and are ascribed to transitions to C+ (2p) + Q" (2p), c"'' (2p) +

(^P)^ C"*" (^P) +0 ('d) and C+ (2p) + ('s). 0+ was not observed in

photolonizatlon, but Is produced by electron Impact Ionization at 24.7

ev [48].

CO, \ = 9OOA 13.79 ev [56]

2 O

There Is a second Rydberg series limit at 69OA, 18.07 ev [56].

Sun and Welssler [55] measured the absorption coefficient In the

range 900A to 374A. Nicole Damany-Astol n, et al., [57] measured absorption to 167A.

Walnfan, Walker, and Welssler [38] measured photolonizatlon cross sections and efficiencies to 473A.

-12-
Welssler^ Samson^ Ogawa and Cook [46] measured photoionlzation

In a mass spectrometer to 430A.

The photoionlzation continuum rises sharply from the threshold to

a = 19 X 10"^ 8 cm^ near 800A and near 690A rises again reaching a flat

maximum near 600A of 32 x lO'lS cm^ (Sun and Welssler [55]) or 29 x

10"18 (Damanay-AstoJn [57]). See figure 18. Damanay-Astoin finds a minimum at 41 5A (29.6 ev) wi th a - 16 x 10'' 8 cm^ [57]^ and o rises

sharply to a broad maximum of 24 x 10"' 8 cm^ near 370A. There is a second sharp minimum of cr » 9 x 10''8 cm^ at 294A (42 ev) and a sharp

rise to a third maximum of o ss 23 x 10"'8 near 270A, From this point

o decreases smoothly to zero at 167A.

Walnfan^et al., find a photoionlzation efficiency ranging from 60

to 100 percent from 900A to 473A. There are many autolonization pealcs

In the range covered.

Mass spectra show 0''' Increasing to a peaic at 646A (19.2 ev) at

6I0A (20.3 ev) and at 556A (22.3 ev) . The cross section at 63OA for

a (0+) Is about 1.4 x 10"'8, cO''" appears near 636A (19.5 ev) and

increases at 6O5A (20.5 ev). The cross section at 63OA is c (C0+) =

.3 X 1CP8 cm2^ Appearance potentials of D+ at 19.2 ev and at 22.3 ev are correlated with processes, CO + 0+ (^S) and 0* (^D) . The two

appearance potentials of CO"*" could be ascribed to CO"*" + 0" (^P) and

CO"*" + (^P) but there is some excess l<lnetlc energy [46].

NO \q » 1340A 9.25 ev [58]

There are also Rydberg series limits [58] at 87I.5A (14.15 ev),

748. 5A (16.48 ev), 678. 4A (18.19 ev) and 676. 8A (18.23 ev)

Sun and Welssler [60] measured absorption in the range 1800A to

374a, and Granler and As to In [63] extended the range to I5OA.

Watanabe [59] measured photoionlzation with a continuous source,

and good resolution showing separate vibration states of NO and NO"**. See figure 19. Walker and Welssler [61 ] measured photoionlzation efficiency to 640A.

Welssler, Samson^ Ogawa and Cook [46] measured photoionlzation in

a mass spectrometer.

The photoionlzation continuum" Increases almost linearly except for

vibration fine structure from 1340A to a value of 18 x 10"'8 cm2 pear

9OOA, droDS to about 8 x 10"' 8 near 780A^ rises to a flat maximum of

20 X 10"'° near 6OOA, drops to 13 x 10" '8 at ^08A, rises to a maximum

of 20 X 10"'8 near 260A and falls to 12 x 10"'8 near 200A. There are

autolonization peaks In most of this spectrum. Figure 20 gives the

spectrum to 3OOA.

-13-
O"*" appears near 636A (19.5 ev), reaches a flat maximum near 620A

and rises again at 600A (20.7 ev) to a second flat maximum. The 0"*" current Is at the maximum about 2 percent of the NO"*" current In this

range. N"*" appears at 570A (21.8 ev) and rises to a maximum near ^kO/K

of about 5 percent of the NDJ*" current. 0"^ probably comes from the dissociation into 0"*" (^S) + N (^S) and N (^D) at 19.5 ev and 20.7 ev respectively. N+ comes from N"*" (^P) + (^P) [46].

N,0 \ = 961A 12.94 ev [62]

2 O

Other Rydberg series limits give energy levels of 16.39 ev, 16.55

ev and 20.10 ev [62].

Astoin and Grainier [64] measured the absorption to I6OA.

Walker and Welssler [6l] measured the photoioni zation efficiency

and cross section In the range 96OA to 687A. Welssler, Samson, Ogawa

and' Cook [46] measured the mass spectrum of the photo ion I zation

products.

The photo ion I zation continuum rises sharply from the threshold to

a flat maximum near 700A of 32 x lO'lS cm^ [64], or 30 x 10"! 8 cm^ [61],

There is a minimum of 17 x 10"'° cm^ near 500A, a second flat maximum

near 36OA of 30 x 10"'° cm^^ a wel 1 defined minimum at 263A of about

13 X 10"'° cm^^ a third maximum of the same size near 300A and the

absorption drops to 4 x lO"'" at I6OA. There are many autoioni zation

peaks in the entire range. See figure 21. NO"*" begins near 810A (15.3

ev) and rises rather irregularly to a value at 65OA of 1.3 times the

N2O"*' current and remains about 30 percent greater than N2O+ to 500A.

N2''" appears near 71 OA (17.4 ev) and rises abruptly to a value about 16

percent of N2O''" and remains of this magnitude to 5OOA. N"*" appears at

62OA (20.0 ev) and is roughly 10 percent of N20'*". O"*" appears near 810A,

15.3 ev and is roughly 10 percent of N20'*". See figure 22.

NO2 Xq = I27OA 9.78 ev [65]

Nakayama, Kltamura and Watanabe [65] measured the photoioni zation

from the threshold to IO8OA. Welssler, Samson, Ogawa and Cook [46]

measured the mass spectrum in the range llOOA to 500A.

Nakayama, et al., find the ionization efficiency very low (.03 to

2 percent) at \ greater than 1200A. There Is an Increase in the

ionization continuum at 1145A (10. 83 ev) . Near 1 lOOA o\ Is about 2.2 x

10-18 07,2.

Welssler, et al., find both N02"*^ and NO"*" appearing near llOOA

(11.3 ev). Beyond 950A, NO"*" becomes greater than NO2"*" and at 645A Is

3.5 X N02^. Both NO2'*" and NO"*" curves show 5 or 6 sharp peaks In the

range llOOA to 5OOA. Four of these seem to be common to both curves. They may well be autoioni zation peaks, but this is an opinion of the

rev I ewer. -14-
0"'' appears at I7.6 ev (700A) and rises to a value of about .75 x NO2* *t 645A. Welssler, et al., do not give absolute values of o for

these Ionization processes. There Is conflicting evidence as to the

first Ionization potential In electron impact research [48] as well as

in these experiments. Nakayama^ et al.^ suggest that 10. 83 ev may be

the appearance potential for NO2 ~* NO* and 0". Weissler, et al., give

this as 1 1.3 ± .4 ev.

H^O Xq = 986A 12.59 ev [66]

Watanabe [66] measured the photoionlzatlon threshold. Nicole

Astoln [67] measured the continuous absorption coefficient in the range

986A to I6OA. There Is banded absorption superposed on the continuum.

Wainfan^ Walker and Welssler [38] measured the photoionlzatlon efficiency

and cross section in the range 986^10 450A. The efficiency is about 40

percent In the range 986A to 900A, and from 950A to 450A is from 70 to

100 percent. cr| rises at a fairly constant rate to 20 x 10"'° cm^ near 625A [38], See figure 23.. Nicole Astoln finds for CTg a value of 21 x

10"' 8 cm2 at 625A. It drops to a sharp minimum of 1 1 x 10"' ^ at 51 2A

and rises to 28 x 10-18 cm^ at 435A and falls to 2 x 10"'8 cm^ at 167A.

The experimental uncertainties are about 20 percent. Mass spectra of

the Ions have not been studied.

CHj^ Xq = 955A 12.99 ± .01 ev [66]

Watanabe [66] has measured the photoionlzatlon threshold. Sun and

Welssler [68] and DItchburn [69] have measured the continuous absorption

to 400A and 300A respectively. Wainfan, Walker and Welssler [38] have

measured the efficiency of photoionization and the photoionlzatlon cross section to 5OOA.

The efficiency of ionization Increases from to 100 percent between

955A and 8OOA. o\ rises sharply to a flat maximum of 39 x lO''^ cm2,

44 X 10-'8 cm^ or 60 x 10"'° near 8OOA using measurements of Sun and

Welssler [68], DItchburn [69] or Wainfan, Walker and Welssler [38]

respectively, and the ionization efficiency data of the latter. o\

decreases regularly with decreasing wavelength to 13.1 x 10-'8 cm^ at

374a and 4 x 10"'^ cm^ at 278A according to DItchburn (Sun and Weissler

give a nearly equal value at 374A) . See figure 24.

The mass spectrum of photoionlzatlon products has not been studied.

The CTj (x) curve is simpler than those found for the diatomic and triatomic molecules with no evidence of autoionization states or higher

Ionization potentials.

-15-
4. SUMMARY

It is evident that much more research is needed In the field of

photo ionization of atoms- and simple molecules. Thus, while some worl<

has been done on all the alkali vapors, only in the case of sodium do

the measurements extend far enough to permit an estimation of the f

number of the continuum. There is some data on all the rare gases

except xenon and something on four other elements. In the case of

molecules, the reviewer has limited this report to a few common gases.

There are data on photoionization thresholds for several hundred polyatomic molecules [67] and in some cases there are measurements of cr from the threshold to about lOOOA.

Quantitative measurements of autoionization transitions are a matter of research interest but it requires a continuous spectrum

emission source to measure the integral of cj across the line, and

such measurements have not been extended into the far ultraviolet. In some atomic spectra and in nearly all molecular spectra the autoionization

peaks interfere seriously with measurements of the continuum. Good reso- lution is necessary to distinguish the continuum from the autoionization

peaks and In complicated spectra photographic methods seem to afford the

most conclusive data in spite of the Inherent limitations of photographic

densitometry. However, electrical methods and mass spectrometry are

required to interpret the results in the case of molecules.

The magnitudes of the photoionization cross sections and the

variation with wavelength show a wide varl atlon. Thus, for atoms, cr near the threshold ranges from .012 x 10"lo for potassium to 36 and

37 X 10"'° for argon and krypton. The figures Illustrate the wide

variation in the shape of the curves of a versus wavelength.

-16-
5. REFERENCES

Welssler, G. L., Handbuch der Physlk 2J_, 306-341 (Springer,

Berlin, 1956).

Bothe, W., Handbuch der Physlk, 2nd Ed. 23/2, p. 8 (Springer,

Berlin, 1933).

Gaydon, A. G., Dissociation energies and spectra of diatomic

molecules, (John Wiley and Sons, New York, (19^7).

Beutler, H., Z. Physik86, 495-515 (1933).

Johnson, F. S., Watanabe, K. and Tousey, R., J. Opt. Soc. Am. 41_,

702-8 (1951).

Wainfan, N., Walker, W. C. and Welssler, G. L., J. Appl . Phys. 24,

1318-21 (1953).

Foote, P. D. and Mohler, F. L., Phys. Rev. 26, 195-207 (1925).

Mohler, F. L. and Boeckner, C, J. Research NBS ^ (1930) RP186^.

Terenin, A. and Popov, B., Physlk Z. Sowjetunion ^^ 299-318 (1932).

Hurzeler, H., Inghram, M. G. and Morrison, J. D., J. Chem. Phys. 28,

I, 76-82 (1958).

Moore, Charlotte E., Atomic energy levels, NBS Circular 467, Vol. 1 (1949), Vol. 2 (1952), Vol. 3 (1958).

Watanabe, K., Nakayama, T. and Mott'l, J., Final report on ionization

potentials of molecules by a photolonization method, OOR No. 1624

(Dec. 1959).

Lassettre, E. N., et al., Ohio State University Research Foundation

Reports to AFCRC, Reports 1 to 1 2 (1953 to 1958).

Sugiura, Y., Scl . Papers Inst, of Phys. and Chem. Research (Tokyo)

II, 1-80 (1929).

Tunstead, J., Proc. Phys. Soc. (London) A66, p. 304 (1953).

DItchburn, R, W., Jutsum, P. J. and Marr, G. V., Proc. Roy, Soc.

(London) A219. 89-101 (1953).

Hudson, R. D., Am. Phys. Soc. Bui. 2, S, 495 (I960); A project

report to AI r Force Research' Center (June 28, I960) unpublished.

DItchburn, R. W., Tunstead, J. and Yates, J. G., Proc. Roy. Soc.

(London) A181. 386-399 (1942-43).

Mohler, F. L. and Boeckner, C, J. Research NBS 1, 303-314 (1929)

RP96.

Lawrence, E. 0. and Ediefson, N. E., Phys. Rev. ^k, 233-242 and

1056-1060 (1929).

Beutler, H., Z. Physlk ^L '31-150 (1934).

Braddick, H. J. J. and DItchburn, R. W. , Proc. Roy. Soc. (London)

A150. 478-486 (1935).

Beutler, H. and Guggenheimer, K., Z. Physlk 88, 25-42 (1934).

DItchburn, R. W. and Marr, G. V., Proc. Phys. Soc. (London) A66,

655-656 (1953).

DItchburn, R, W. and Hudson, R. D., Proc. Roy. Soc. (London) A256.

53-61 (I960).

Jutsum, P. J., Proc. Phys. Soc. (London) A67 . 190-191 (1954).

Marr, G. V., Proc. Roy. Soc. (London) A224. 83-89 (1954).

Beutler, H. and Demeter, W., Z. Physlk £1^ 143-150 and 202-217 (1934),

Garton, W. R. S., Nature 166. p. I50 (1950).

-17-
[30] Marr, G. V., Proc. Phys. Soc. (London) A62, 196-197 (195^).

[31] Po Lee and Welssler, G. L., Phys. Rev.

^

5^0-5^2 (1955).

[32] Axel rod, N. N. and GIvens, M. P., Phys. Rev. 115» p. 97 (1959).

[33] Dershem, E. and Schein, M., Phys. Rev. XL 1238-12^5 (1931).

[34] Wheeler, J. A., Phys. Rev. JtL 258-263 (1933).

[35] Po Lee and Welssler, G. L., Proc. Roy. Soc. (London) A220, 71-76

(1953).

[36] DItchburn, R. W., Proc. Phys. Soc. (London) J^ 461-462 (I960).

[37] Beutler, H., Z. Phys Ik

^

177-196 (1935).

[38] Walnfan, N., Walker, W. C. and Welssler, G. L., Phys. Rev.

^

542-549 (1955).

[39] Pery-Thorne, Anne and Gar ton, W. R. S., Proc. Phys. Soc. (London)

26, 833-843 (I960).

[40] Beutler, H. and Demeter, W., Z. Physlk^ 218-229 (1934).

[41] Po Lee and Welssler, G. L.,. Astrophys. J. 115. 570-571 (1952).

[42] Schonhelt, E., Z. Naturforsch. 15A, 9, 841-842 (I960).

[43] Beutler, H. and Junger, H. 0., Z. Phys Ik 100, 80-94 (1936).

[44] Welssler, G. L., Po Lee and Mohr, E. I., J. Opt. Soc. Am. 42,

84-90 (1952).

[45] Curtis, J. P., Phys. Rev. ^ib 908-910 (1954).

[46] Welssler, G. L., Samson, J. A. R., Ogawa, N. and Cook, G. R.,

J. Opt. Soc. Am. 4a, 338-349 (1959).

[47] Tanaka, Y. and Takamlne, T., Scl. Papers Inst. Phys. Chem. Research

(Tokyo)

^

427-436 and 437-446 (1941-42).

[48] Field, F. H. and Franklin, J. L., Electron Impact phenomena

(Academic Press, New York, 1957).

[49] Welssler, G. L. and Po Lee, J. Opt. Soc. Am. 42, 200-203 (1952).

[50] Po Lee, J. Opt. Soc. Am. 4^ 703-709 (1955).

[51] Watanabe, K. and Marmo, F. F., J. Chem. Phys. 1^ 5, 965-971 (1956).

[52] Tanaka, Y., Scl. Papers Inst. Phys. Chem. Research (Tokyo) 3,9 . 467-474 (1941-42).

[53] Takamlne, T., Tanaka, Y. and Iwata, M., Scl. Papers Inst. Phys.

Chem. Research (Tokyo) 40, 371-378 (1942-43).

[54] Watanabe, K., J. Chem. Phys. 26, 3, 542-547 (1957).

[55] Sun, H. and Welssler, G. L., J. Chem. Phys. 2^, S, 1625-1628 (1955).

[56] Tanaka, Y., Jursa, A. S. and LeBlanc, F. J., J. Chem. Phys. J_2, 4,

1199-1205 (I960).

[57] Damanay-Astol n, N., Sanson, L. and Bonnelle, M. C, Compt. Rend.

250. 10, 1824-1826 (I960).

[58] Tanaka, Y., Scl. Papers Inst. Phys. Chem. Research (Tokyo) 39.

456-466 (1941-42).

[59] Watanabe, K., J. Chem. Phys. 22, 9, 1564-1570 (1954).

[60] Sun, H. and Welssler, G. L., J. Chem. Phys. 2^, 1372-1373 (1952).

[61] Walker, W. C. and Welssler, G. L., J. Chem. Phys. 2^, p. 1962

(1955).

[62] Tanaka, Y., Jursa, A. S. and LeBlanc, F. J., J. Chem. Phys. 28,

350-351 (1958).

[63] Granier, J. and Astoln, N., Compt. Rend. 242. 1431-1433 (1956).

[64] Astoln, N. and Granier, J., Compt. Rend. 241. 1736-1738 (1955).

-18-
[65] Nakayama, T., Kitamura, Y. and Watanabe^ K., J. Chem. Phys. ^Oj Sf

1180-1186 (1959).

[66] Watanabe, K., J. Chem. Phys. 26, 3, 5^2-547 (1957).

[67] Astoin, N., Compt. Rend. 242, 2327-2329 (1956).

[68] Sun, H. and Weissler, G. L., J. Chem. Phys. 2^ 6, 1160-1165 (1955)

[69] DItchburn, 'R. W., Proc. Roy. Soc. (London) A229. 44-62 (1955).

-19-
c

-H

c:

r-t a>>

in

09 M- •P o H

P c > o c •M s

o

0) +> (/I O

0) U) H (/) W o

vo c

o

-H c

13 oM

fH Q.

0) I_ a o w w^

c (D B (J o •— s: E

f^ O

+J

fD in (U • j:

in 1-

01

in

qw UT WOT^oas ssojq uof^daoeqv

20
2400

Wavelength in A

2000 1600 1600 1400 1200

r

HIO

c

o

•HP

O

0) CO

CO09

c

o

P

o

a

3

_10.0

a

•p

o

<UOO

co

p

&

o

CO <

6 7 8 9 10

Photon Energy - Electron Volts

11

Figure 2. The atomic absorption cross section of sodium [17^18]

21
mo ^UQfotJJsuO uoT^dJOsqv

c

X!•P

0)>a

IS

00

E

3

(/)

(rt tD M

o

CL

CO y- 4d O

rHo c > O

G

2P

4-1 o

0) O (O 0) (/> H o H uu

1 c

fe o u M

Q) Q.o C

B o o

£ §

+j

«D

(U ^

3

qw 2-OT «T uoTi^oag seojo uoTc^dJogqv

22
09s

o09

CO

o

•iH

-P

o

o

COO

u

o

2800 2600

wave-length (A)

2400

Figure k. The atomic photoioni zation cross section of rubidium [19]

23
mo ^uaTOTJjeoo uoT^daosqv

o

<

s

4)

0)>

01 •PiHO

>

oh

p

O

0) rHw

I

sM

O

+3O

s:

egE

(Au

co

o

O

a.

i-o

(/)

(U

QW 2-OT uf uofi^oas egoao uoTi^daosqv

24
in^

•

1—

-*

CJ

i—iE3

•MB«n

<U o

c

en o

id E

4-O

ymm^ c ts

oM

o

.f~ .«J xxo V) o c O

t/^ O) i- tn— — o

O)>^

co ^

Q.U

O

WJ ^

<DU

*«• o E

O

CD M

(0

0) f1-

•

0)

1- ^ 3

O)

y3

(jUJO) ^fi\xuo\v^s SSOJO uondjosqv

25
oooo

00 II o I i i i I I <C '^ c^ co

•^Ma

g k_ o o u tn

<+- jQ E3 (U

•.. c O .—

*-« ^—

OJo

J3

<+-o C • o 1—

c LA o M 04

1— (D 1 1 M N O .— E

(D

C 3

Wl o 3C

W) o

u»

M •M

O 3 C

1- (D o o

CD o c C r_ o ._ r— 5 (U M O F

Q.JC tn

L. «i o (D

tf) < JO o c

(0 o o o '" 13

0) E o (/) o M o

+j a.

»D < I. 00 0)

Q> Csj Q. x: o 3

\- CM (/) m rN.

0)L.3

a>

26
o

o

o

oo

o

CO "^

1-* ^

tS)

fl<D 1—

<D o > o a

^

E3

"o

r«»(0u

11-o

co

•Mo

0)lA

(A

(Ao

1-o

co • *^ 1—

+J urv a. cs

1- 1—

o

<A < J3 o (Q COo O

«^g o

o M

•M

(D <

o 0) j: vo

1- •-"

• 00

0)u

o>

(qj\[) noT(^oas-8SOJO uoic^djosq'B

27
^ "<

f

6

I

CM

co

c o —

<0 10 Nc

(U o — •-:• c

E

3

(U 10

O C— >

c -o o «- — o

+j

U (U

(O +J

CT> c

o

Q.

(/» <t l_ lO O O

O Lf\ CO

I- -* J3 U — (D COO)

O M c

•^ < —

Q.O

J- o E

O r^ O

lO —

<T> E

O J- — >4- E

O <

3 -C

CM

(/) I I

0) "a

0) (D Q. ••-• (D

0) o

0) ._

-ac

3

(gUIOgx-Ol) UOTC^OQS-SSOJO OTUIO^^'B

28
o (A

0)to

U)O -D

1- C

OJ

0) E b > 5 ^—^ i_ I- 3 <+- U

• (/) E "O -M 3 0) O ~ ^ T3 — W)

0) «D "O -C -o C

0)1—

> c«j 31—

O

o —

V)c

.— (DO)

4- (J >

(1) o

(1)

o

oco

4-1 a.uO

(0

C

(D

I O ro

Q) —

0) u < —

E tf) O —

O i- 0) to 4- 3

0)

1-3

cn

(dXSlD) ,wo uj (>«) lN3IOUd300 NOIldHOSav

29
vO

c

I-3

o

EO

co

0)

co

o

0)

(/>

(A

v>o

oc

o

o

lA

(0

0) I0)3

(uqui) I?

30
d6pd.

d6pd. 

-^ Turv

0)

CA

(ACCoc

0)Oco

•MQ.O

I/)

0)

CM

a>3

31
oooo X X

UJ UJ ooS

<* » I L ooo

oo co

•^M

o.uo

lA ^

(DW • Di—

O m3 CO

Ci—

•^

4-1 c c o o +j o u

(0

L. o o

M- oc

+J (D c

(U 0)c

"o

uo

M- x:

M- t-

<U 1 O >• O \-

0) c o. o

•««

p

•M

Q

Q. L. u M- O

(A

C

XI o

(D

Ma

0) >. £ u

1- J>£

CO

(,.UJ3) X>

32
coNac

tocoo

en Si

toco

•MO

0) . in 1—

tn -^ (n CO O r<-» »- ^

(J

—

J1- I I to — c 3 (U o en

0) o i

j_ o -o E >.

to

JSZ c

0)3

cn

33
Mb

SO

¥0

30

20

10

10^

N.

X

hy -^

iZfY 75,5

I.

20,7 3/,<? ev €2,0

X

IPi

4

\

%! IVe/sSter etaC//S5Z,)

^ ; iVaintan efa/. (tsssj/e^^ _

IP,

.^

X

/^^

=:^Z7

-SOO

¥00

200

1200 1000 soo 600 ¥00 200

Figure 15. The molecular cross section for absorption and ionization

in nitrogen [44, 38, l].

34
—

cON

TOC

(0coo

inO

**-co

(J

(A

Ul I 1 tn i

O ^

I- CO

I- o <o irv .— I I 3o c

0) 0) oE

(1) o

vO

a>3

35
o 8 ooo

6^o

in oo

a:

fO

l-Kl-f-M- b

r— O

lO

—r— O o

CM

—1~ o o

h8 <Xo

UJ

_l

UJ

0) uT3 <U • ^ ^* Xo »- c a> O CL E Q.3 CO C

JQ

—

1-

(0 tn O 0)c

u-

—

O

—

C -l-" O s- — O M x: o v>

0)in •

(/>! 1

t/i lA O Lf\ V-l 1 O E C 3 O 3 — C

4->—

CL-M

«-

C o o • en o in ^ {= (0 in d) •— 4-) L. m

(D 0) >^ — > in 3 l- O 3 D

0)

O c

w-^ (0 O "o X) E 0) +J 5

0) !-> o

-C o x:

hQ (/) • r>.

a>

i-3

O)

36
o

LU

_J

LUI

W)5 • o

(U -C

•a (rt •^X (U o >o o < co

J3 • 1- 1—

fO LA o LA

<4-o E3 c 3 o C ^ •^

+J +J u C

(U o

Irt o

Irt c

1/1 o ou •M o <0N c •^ o C — o

4-) •— • a. t/) u. l/> F o .— 0)

I/) +J XI 0) <A

fU > > l_ (/) L. 3

ro o TJ

r—

C 3 TJ to O <U ^ (U M

,— l-> o o O 5

z: o M

003

cn

37
sol

id

curve

].

Arrows

o

o

LA

Ci J lO o

sorpti

oxide

.^^ ^ O

< to —

"^ t- 4-> o X

o —

4- C

•n H • CM O -in c 0) ^* z

C — 1- O 3

llJ — .-». -M _J +J W) o

liJ a> o i- > W "D +J <

ross ion (

ion

s

o O 4J •!-» o (0 (0 CM U N L.

Mol

ecu

la

and

ioni

show

vib

o\

0)

1.3

cn

(^UJOqiJOI) N0I133S SSOdD

38
^-^ cONCocco

a.

i-o

(0

I- 1—

o — C 0) o — — o +J .— o >

(U fD +J

(rt

—in 3 o

\- l_ U (D

l_

(0 c o o oCM3

39
60Q.0O0 soojyoo IfiOJiQO 300000 lOQOOO lOOjOOO

V cm-'

Figure 21. Molecular absorption coefficient of nitrous oxide as a function of wave number. Dashed curve is continuous

absorption. (Astoin and Granier [64].)

40
12.4 13.8

PHOTON ENERGY

15.5 17.7 20.7 24.8 ev

1000

WAVELENGTH

400A

Figure 22. Ions produced by photoionization of nitrous oxide in a mass spectrometer [46].

41
-^«/

N

*Co

*oMo

Q. T>c

IDO

10MCou • 0)1—

«n

—I I vt

(/)u

O

O

>- Q.>

1-

ro »- — 0) D -M O (D

0) 5

CM3

42
-<^ c • o — .- (D M

<0 -M N 0) C ^ O C — (D O ^ 4-" C O — c o O (D — "D .—

M

Q. cn >»

I- c o O — C

tf) tf> 0)

(D

U I—I •—

t- <y\H- o VO MM- I Id) c c c O I- o — 3 ._

*-> ^ -u O JZ <0

(UU

N

(/) -M .—c

tn o o

tf)

—

Oo . o

«- c Q.

<D as — sz c 3 +j o U (U 0) El—

— 00 O M- cr\ z: oi—

CM3

cn

CA

(^h) ^-O -io '-o

43

V. S. DEPARTMENT OF COMMERCE

Luther H. Hodges, Secretary

NATIONAL BUREAU OF STANDARDS

A. V. Astin, Director

THE NATIONAL BUREAU OF STANDARDS

The scope of activities of the National Bureau of Standards at its major laboratories in Washington, D.C., and

Boulder, Colorado, is suggested in the following listing of the divisions and sections engaged in technical work.

In general, each section carries out specialized research, development, and engineering in the field indicated by

its title. A brief description of the activities, and of the resultant publications, appears on the inside of the

front cover. WASHINGTON, D.C.

Electricity. Resistance and Reactance. Electrochemistry. Electrical Instruments. Magnetic Measurements.

Dielectrics. High Voltage.

Metrolog)'. Photometry and Colorimetry. Refractometry. Photographic Research. Length. Engineering Metrology.

Mass and Scale. Volumetry and Densimetry.

Heat. Temperature Physics. Heat Measurements. Cryogenic Physics. Equation of State. Statistical Physics.

Radiation Physics. X-ray. Radioactivity. Radiation Theory. High Energy Radiation. Radiological Equipment.

Nucleonic Instrumentation. Neutron Physics.

Analytical and Inorganic Chemistry. Pure Substances. Spectrochemistry. Solution Chemistry. Standard Refer- ence Materials. Applied Analytical Research.

Mechanics. Sound. Pressure and Vacuum. Fluid Mechanics. Engineering Mechanics. Rheology. Combustion

Controls. Organic and Fibrous Materials. Rubber. Textiles. Paper. Leather. Testing and Specifications. Polymer Structure. Plastics. Dental Research.

Metallurgy. Thermal Metallurgy. Chemical Metallurgy. Mechanical Metallurgy. Corrosion. Metal Physics. Electrolysis and Metal Deposition.

Mineral Products. Engineering Ceramics. Class. Refractories. Enameled Metals. Crystal Growth. Physical

Properties. Constitution and Microstructure. Building Research. Structural Engineering. Fire Research. Mechanical Systems. Organic Building Materials. Codes and Safety Standards. Heat Transfer. Inorganic Building Materials. Applied Mathematics. Numerical Analysis. Computation. Statistical Engineering. Mathematical Physics, Operations Research. Data Processing Systems. Components and Techniques. Coii^)uter Technology. Measurements Automation.

Engineering Applications. Systems Analysis.

Atomic Physics. Spectroscopy. Infrared Spectroscopy. Solid State Physics. Electron Physics. Atomic Physics.

Instrumentation. Engineering Electronics. Electron Devices. Electronic Instrumentation. Mechanical Instru- ments. Basic Instrumentation. Physical Chemistry. Thermochemistry. Surface Chemistry. Organic Chemistry. Molecular Spectroscopy. Molecular Kinetics. Mass Spectrometry.

Office of Weights and Measures. BOULDER, COLO.

Cryogenic Engineering. Cryogenic Equipment. Cryogenic Processes. Properties of Materials. Cryogenic Technical Services. Ionosphere Research and Propagation. Low Frequency and Very Low Frequency Research. Ionosphere Research.

Prediction Services. Sun-Earth Relationships. Field Engineering. Radio Warning Services. Vertical Soundings Research. Radio Propagation Engineering. Data Reduction Instrumentation. Radio Noise. Tropospheric Measurements.

Tropospheric Analysis. Propagation-Terrain Effects. Radio-Meteorology. Lower Atmosphere Physics.

Radio Standards. High Frequency Electrical Standards. Radio Broadcast Service. Radio and Microwave Materials. Atomic Frequency and Time Interval Standards. Electronic Calibration Center. Millimeter-Wave Research.

Microwave Circuit Standards. Radio Systems. Applied Electromagnetic Theory. High Frequency and Very High Frequency Research. Modulation

Research. Antenna Research. Navigation Systems.

Upper Atmosphere and Space Physics. Upper Atmosphere and Plasma Physics. Ionosphere and Exosphere

Scatter. Airglow and Aurora. Ionospheric Radio Astronomy.
NBS