Photoelectron spectroscopy of CH2N

Daniel C. Cowles, Michael J. Travers, Jennifer L. Frueh, and G. Barney Ellison

Citation: The Journal of Chemical Physics 94, 3517 (1991); doi: 10.1063/1.459773
View online: http://dx.doi.org/10.1063/1.459773
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Photoelectron spectroscopy of CH
2
N-
Daniel C. Cowles, Michael J. Travers, Jennifer L. Frueh, and G. Barney Ellison
Department of Chemistry and Biochemistry, University of Colorado. Boulder, Colorado 80309-0215
(Received 29 June 1990; accepted 31 October 1990)
We have measured the negative ion photoelectron spectra ofCH
2
N- and CD
2
N- and find
the electron affinities: EA(CH
2
N) = 0.511 0.008 eVand EA(CD
2
N) = 0.498 0.011 eV.
Franck-Condon simulations of these spectra are carried out and we estimate the CH
2
N- and
CH
2
N geometry differences; we fit our spectra with the following [constrained] molecular
structures:
H 1.106 A
118 "C= N
/ [1.27 A]
H
We combine our EA (CH
2
N) with the results of previous gas phase ion studies to extract a
number of thermochemical parameters (kcal/mol): Dg (CH2N-H) = 85 5,
Dg (H-CHN) = 23 6, Dg (H
2
C N) = 144 6, and the isomerization enthalpy of
H
2
CN + ..... HCNH + is ilH
isom
(C
2v
..... C
oov
) = - 51 7. Attempts to calculate the geometry
and vibrational frequencies of the H2 CN radical are disappointing. Unrestricted Hartree-Fock
and second-order M!6ller-Plesset ab initio calculations in a 6-31 + + G** basis produce badly
spin-contaminated wave functions which do not reproduce the experimental findings.
I. INTRODUCTION
We report a study of the photoelectron spectrum of the
negative ion isoelectronic with formaldehyde, CH
2
N - .
Photodetachment of CH
2
N - ion beams gives us the elec-
tron affinity of CH
2
N and allows us to examine the spectros-
copy of this reactive radical. Most of the structure in our
photoelectron spectrum arises from excitation of vibrations
and rotations in methylene amidogen, CH
2
N:
CH
2
N - + Wo ..... CH
2
N(v,J) + e- (KE). (1)
In addition to being interesting in its own right, the elec-
tron affinity is a link in many clever thermochemical cycles. I
Negative ion photoelectron spectroscopy permits a measure-
ment of the radical electron affinity, EA(R); gas phase ion
chemistry uses proton transfer reaction kinetics to deter-
mine the hydrocarbon gas phase acidity, (RR).
These values may then be combined to extract the homolytic
bond dissociation energy, D (RR) :2,3
D(RR) = (R-ll) + EA(R) - IP(R). (2)
Use of Eq. (2) with established hydrocarbon acidities and
electron affinities provides one with a comprehensive picture
of the thermochemistry of Ii system of related species.
4
In
this case, we use EA (CH
2
N) and the proton affinityS of
CH
2
N- to extract D(CH2N-H). This bond strength per-
mits us to deduce both the heat of formation of the methy-
lene amidogen radical and the C-H bond strength,
D(H-CHN).
Methylene amidogen predominates in the reaction of N
atoms with CH
3
radicals
6

7
and is formed by the addition of
H atoms to HCN.
(3)
Methylene amidogen is also conjectured to be one of the
primary pyrolytic products
8
of the explosive, cyclic nitra-
mines, RDX and HMX:
(4)
Loss of one or two hydrogens from the intermediate CH
2
N
radical leads to the stable species, HCN and CN.
The CH
2
N radical was detected some time ago by EPR
spectroscopy9 among the photolysis products of HCN iso-
lated in an argon matrix. EPR techniques were later used to
observe CH
2
N in an assortment of r radiolysis studies 10 and
in a discharge of protons and solid HCN. II These magnetic
resonance spectra provided conclusive evidence for equiva-
lent protons in CH
2
N and established the radical as a C
2v
species. There is an important paper
lO
which discusses the
EPR spectra of CH
2
N and the unusually large hyperfine
coupling constants for the H atoms, roughly 87 G. Hyper-
fine constants of this magnitude imply that each proton is
strongly coupled to the radical center on N and indicate an
unusually short C=N bond and a powerful, hyperconjuga-
tive interaction of the in-plane a-like radical with each of the
electron pairs of the C-H bonds. An in-plane a radical 10-
cated on the nitrogen atom is certainly consistent with all of
the EPR studies that have been published:
9
-
11
J. Chern. Phys. 94 (5), 1 March 1991 0021-9606/91/053517-12$03.00 1991 American Institute of Physics 3517
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3518 Cowles et al.: Photoelectron spectroscopy of CH
2
N-
(5)
We anticipate
12
a photodetachment transition from a
closed shell CH
2
N - ion to aCT-type CH
2
N radical as depict-
ed in Eq. (5).
This process is analogous to the photoionization of formal-
dehyde.13
Ion-molecule chemistry studied in a flowing afterglow
device and an ICR has contributed much to our understand-
ing of the thermochemistry of the CH
2
N system. In a sur-
vey14 of the ion chemistry of CH
2
N-, (CH2N-H)
was reported as 388 5 kcallmol while the EA(CH
2
N)
was bracketed around 0.5 0.1 eV. Preliminary photode-
tachment studies 15 of the CH
2
N- ion suggested an
EA(CH
2
N) 0.05 eV. In an ICR spectrometer
16
the gas phase chemistry of HC==NH + was used to fix the
heat offormation of methylene imine. By detecting the posi-
tive ions, the following reactions were monitored:
HC==NH+ + 2-methylpropane-+no reaction + 2-methylbutane-+no reaction
The neutral product resulting from hydride transfer to
HC==NH + reaction is undoubtedly CH
2
NH. Based on the
hydride affinities of2-methylbutane and methylcyclohexane
it was possible to bracket the heat off ormation of the imine,
tlllJ298 (CH
2
NH) = 26.4 3.2 kcallmol.
Recently the ionization potential of CH
2
N has been
measured
17
in a series of electron impact and synchrotron
threshold experiments; IP(CH
2
N) = 9.4 0.1 eV and
IP(CD
2
N) = 9.4 0.1 eV. These are important measure-
ments since they allow us to calculate the heat of formation
of the C
2v
cation, CH
2
N + .
CH
2
N is the subject of a number of recent ab initio cal-
culations. The structures of the CH
2
N - ion and CH
2
N ra-
dical are predicted by a Hartree-Fock calculation in a 6-
31 + G** basis; second-order M011er-Plesset correlation
corrections to the HF energy are used to estimate
EA(CH
2
N) aofO.3 eV.
18
In a separate study, GVB-CI tech-
niques are used to scrutinize the potential energy surface for
reaction (3) and the relative product energies and reaction
barriers are calculated. 19
Most recently, an infrared absorption spectrum of ma-
trix-isolated CH
2
N was obtained and most of the vibrational
modes identified.
20
Several of the properties of methylene
amidogen are collected in Table I. An extensive review ofthe
molecular properties of the CH
2
N radical has recently been
published. 21
II. EXPERIMENTAL
The instrumentation we use to carry out these experi-
ments has been described in some detail elsewhere.
22
.
23
Briefly, ions are prepared in a conventional dc electric dis-
charge at a pressure of approximately 0.1 Torr. The CH
2
N-
ion is produced in a discharge of methyl azide (CH
3
N
3
) and
N
2
0 where a 0.015 in. diam. tungsten wire filament serves as
the cathode; weak ion beams of the deuterated ion, CD
2
N - ,
could be produced from a discharge ofCD
3
N
3
, NH
3
, and
N
2
. Note that a different preparation scheme for CD
2
N-
(6)
was necessary due to interference from NO -. Sufficient
quantities of 0 - and NH
2
- ions are created in the respective
plasmas for calibration purposes.
Methyl azide was prepared by the method of Livingston
and Ra0
24
without significant deviation; purification was
accomplished by two freeze-pump-thaw cycles followed by
vacuum distillation. Since methyl azide is highly explosive,
only small amounts ( < 5 g) were prepared as needed.
Negative ions are extracted from the plasma, focused
and accelerated to form a 600 eV beam which is then mass-
analyzed by a Wien velocity filter and delivered to the high
vacuum chamber (10-
9
Torr) for detachment. Typical
mass-selected beam currents for CH
2
N - and CD
2
N - are
300 and 75 pA, respectively.
The mass-selected ion beam is intersected by the intra-
cavity radiation of an Ar II ion laser mounted such that the
plane of polarization of the light beam is fixed at the "magic
angle" (54.7) with respect to the electron collection direc-
tion. Our laser is operating CW on a single line (wo = 488
nm or 2.540 eV) with approximately 75 W of circulating
TABLE I. Established properties for the methylene amidogen radical.
A. Thermochemistry


IP(CH,N)
IP(CD,N)
388 5 kcallmol
26.4 3.2 kcallmol
9.4 0.1 eV
9.4O.1 eV
B. CH, N (Matrix) vibrational frequencies (cm - , )
Mode Symmetry CH, N
V, (CH, sym. stretch) a,
V
2
(CN stretch) a, 1725.4
V3 (CH
2
scissors) a, 1336.6
v. (CH, N umbrella) b, 954.1
Vs (CH
2
asym. stretch) b
2
3103.2
v. (CH, rock) b, 912.8
Reference
14
16
17
17
Ref. 20
CD,N
1073.3
776
2427.S?
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Cowles et 81.: Photoelectron spectroscopy of CH
2
N- 3519
power. A small portion of the detached electrons (10 - 3) is
collected and energy analyzed by a pair of electrostatic hemi-
spheres arranged in series. Spatially dispersed electrons exit
the hemispheres, strike a position sensitive array detector
and are counted. With the aforementioned ion beam cur-
rents we analyze 10-100 counts/s with an operating resolu-
tion of approximately 20 meV (FWHM).
The photoelectron spect rum must be transformed to the
center of mass (CM) reference frame and the energy scale
calibrated with a reference ion. To calculate the CM kinetic
energy ofthe detached electrons we use the following expres-
sion:
KE = KEcal + r( V cal -- V.
lit
) + m W [2. __ 1_] .
M Meal
(7)
In this expression, KE is the CM kinetic energy of the elec-
tron detached from the ion of mass M; V.
lit
is the voltage
through which the electron must be accelerated to reach the
transmission energy of the analyzer (V.
lit
= To - KE). The
kinetic energy scale is fixed by detaching a calibration ion
(KE
eal
= lUu
o
- EA
eal
) of mass Meal with a well-known
electron affinity. We use 0- [EA(O) = 1.461110
0.000 001 eV]ZS and NH; [EA(NH
2
) = 0.771 0.005
800
CH2N
MfZ = 28
Laser 1..0 = 488 nm (2.540 e V)
CIl

600
0
U
Z
0

t3
400
C
r.t:t
0
f-o
0
::t:
rl.
200
D
o
eV]Z6 as calibration ions since they are produced simulta-
neously with CH
2
N- and CD
2
N-, respectively. Veal is the
voltage needed to allow transmission of the calibration ion
electrons; m is the mass of an electron; W is the beam energy
in eV; and r is a dimensionless energy scale compression
factor (typically found to be 1.000 0.005).21 By varying
the value of V.
lit
we are able to sample electrons with differ-
ent kinetic energies.
III. RESULTS
The photoelectron spectra of CH
z
N - and CD
z
N - are
shown in Figs. 1 and 2; Table II is a listing of the CM kinetic
energies of the observed transitions for each of the features in
Figs. 1 and 2. We will argue in the discussion section that
feature A is the (0,0) band of the photoelectron spectrum;
hence this peak furnishes us with the raw electron affinity.
Some corrections must be considered before it is possible to
extract an electron affinity from these data. We must ac-
count for the unresolved rotational transitions which are
blended together in our spectra. In addition, we must pay
attention to any corrections associated with possible spin-
orbit effects and the compression of our energy scale ..
The first correction is due to the unresolved rotational
manifold under each peak. For an asymmetric rotor the
A
B
1.2 1.4 1.6 1.8 2.0 2.2 2.4
CM PHOTOELECTRON KINETIC ENERGY (eV)
FIG. 1. Photoelectron spectrum of CH
2
N - . Data point spacing is roughly 5 meV.
J. Chern. Phys., Vol. 94, No.5, 1 March 1991
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3520
Cowles et al.: Photoelectron spectroscopy of CH
2
N-
150
A
MfZ = 30
Laser 1..0 = 488 nm (2.540 e V)
100
B
c
50
o
1.2 1.4 1.6 1.8 2.0 2.2 2.4
CM PHOTOELECTRON KINETIC ENERGY (eV)
FIG. 2. Photoelectron spectrum of CO
2
N - . Data point spacing is roughly 5 meV.
band centroid is shifted from the rotational origin by an
amount
28
where the rotational constants (A " B " and C' belong to the
radical while A ", B", and C" are those of the ion) must be
approximated. We estimate the rotational temperature of
the ions to be T=. Trot r;;5, TVib = 800 200 K.
I:l. =k T -+- ---
[
A' H' C' 3] (B"-B')
rot B 2A " 2H" + 2C" 2 + 3 '
The second correction attempts to account for the ef-
fects of spin-orbit levels on the determination of electron (8)
TABLE II. CM Photoelectron kinetic energies (eV).
Laser A.
o
= 488 nm (2.540 eV).
CH
2
N CD
2
N Assignment
a 2.200 0.050 2.160 0.060 3
1
1370cm -I 950 em-I
A 2.030 0.006 2.042 0.009 (0,0),2:,3:
1330 em -I 96Oem-
1
B 1.865 0.006 1.923 0.010 3 ~ 2 ~ 3;
1480cm-
'
1080em--
'
C 1.681 0.006 1.789 0.010 n, ~ 1 ~ 3 :
1330em-
1
101Oem-
1
D 1.516 0.009 1.664 0.015 1 ~ 3 ~ 1 ~ 3 l
1450em-
'
101Oem-
1
E 1.336 0.015 1.539 0.020 1 ~ 1 ~ 3 ~
1260 em -I
F 1.180 0.020 1 ~ 3 ~
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Cowles et at.: Photoelectron spectroscopy of CH
2
N-
3521
affinities. In the CH
2
N <-CH
2
N - system [Eq. (5)], the un-
paired electron residing in the "p-like" b
2
orbital of CH
2
N
radical could in principle give rise to spin-orbit states. How-
ever CH
2
N is not a linear spe:cies and the nitrogen p orbital is
clearly in the molecular plane so this is a a radical. Therefore
any spin-orbit correction is difficult to estimate and all we
can do is to widen the error bars on our final values. We add
an uncertainty factor of 0.002 eV to our raw electron af-
finities.
Finally, we consider the errors resulting from the uncer-
tainty in the energy scale compression factor r. The uncer-
tainty associated with our measurement of r
(1.000 0.(05) propagates in Eq. (7) to add an energy-
dependent uncertainty factor to all of our CM kinetic energy
data. For the EA assignments of CH
2
Nand CD
2
N we find
these uncertainty contributions to be 0.005 eV and
0.002 eV, respectively. These corrections, initial and final
values for the EA are summarized in Table III.
IV. DISCUSSION
A. Photoelectron assignments
The photodetachment data for CH
2
N - and CD
2
N -
are displayed in Figs. 1 and 2. The spectra commence with an
intense feature A which shifts only slightly upon deutera-
tion. This identifies the A peak as the (0,0) band in the pho-
toelectron spectra and fixes (Table II) the raw
EA(CH
2
N) = 0.510 0.006 eV and the raw
EA(CD
2
N) = 0.498 O.OlOeV. The weak peakais identi-
fied as a hot band by its shift toward the (0,0) peak upon
deuteration and by the irregular response of this feature to
changing ion source conditions. Thus, the ions sport a vibra-
tion at roughly 1400 cm -I. From the isotope shifts in the
CD
2
N spectrum, it is clear that the active modes involve the
motion of hydrogen atoms. Considering the shapes of the
Franck-Condon profiles in Figs. 1 and 2 we surmise that
detachment ejects an electron that is "somewhat nonbond-
TABLE Ill. Experimental constants.
Raw electron affinity
Rotational correction
Scale compression factor
Spin-orbit factor
Final electron affinity
CH
2
sym. stretch (vi)
CH
2
scissors (v; )
CH
2
sym. stretch (vi')
CH
2
scissors (V;)
CH
2
N
0.510 0.006 eV
0.001 0.001 eV
0.000 0.005 eV
0.000 0.002 eV
0.511 0.008 eV
(11.8 0.2 kcal/mol)
2820cm-
'
l337cm-
1
... cm-
I
1400cm -I
CD
2
N
0.498 0.010 eV
0.000 0.001 eV
0.000 0.002 eV
0.000 0.002 eV
0.498 0.Q11 eV
(11.5 0.2 kcal/mol)
2080cm -I
990cm-
'
... cm-
'
1034cm-
'
Franck-Condon geometries
II 1.195 A
IOI
O
"C=N-
11/ 11.27 AJ
X 1"1
ing." Indeed, expression (5) suggests that the "active elec-
tron" resides predominantly in a nonbonding orbital local-
ized on the N atom. Consequently, we anticipate marginal
excitation of the C=N stretch and H-C-H scissoring mo-
tions (v
2
and V3 in Table I) upon detachment. The peak
intervals in Table II indicate otherwise; feature B is split
from the origin (A) by 1330 cm -1, a result far from the
established value of 1725.4 cm - 1 for V
1
. The vibrational fre-
quencies of Table I strongly suggest that the active modes in
our photoelectron spectra are the C-H stretch (VI) and
H2 C scissoring (v
3
) modes; V
2
seems to be very weak or
absent.
The peaks in Fig. I may now be assigned in a straightfor-
ward manner. A simple progression of the scissoring mode
builds intensity beneath features B, C, D, E, and F. However,
V3 cannot be the only active mode on account of the irregular
intensities of peaks A, Band C. A simple explanation for the
exaggerated intensity of the C peak is the presence of a sec-
ond active mode and the C-H stretching vibration VI is the
only reasonable candidate. This is the single mode in the a I
symmetry block with a frequency in the required range
around C (Table II a.:: 2810 cm -I). Thus, the C feature is a
blend of two transitions, VI and 2v
3
, while D, E and Fare
further permutations ofthis pair of vibrational modes. As far
as we are aware, this is the first observation of the C-H
stretch; the earlier matrix isolation
20
study failed to observe
any transitions involving VI but estimated it at 2999 cm - I.
We model our photoelectron spectra by carrying out an
analysis of the Franck-Condon factors. The Franck-Con-
don factor is the square of the integral over the vibrational
wave functions of ion and neutral.
(9)
In this expression, v' labels the vibrational quantum state in
the CH
2
N neutral and v" the vibrational state in the
CH
1
N - ion. In order for Eq. (9) to be nonzero, the integral
must be totally symmetric with respect to the symmetry
operations of the molecular point group, C
1v
' Therefore only
the a I vibrational modes in the neutral (or even quanta of
the non totally symmetric modes) can be excited by detach-
ment. The Franck-Condon factors are calculated in a varia-
tionally correct manner by diagonalizing the vibrational
SchrOdinger equation [( 10) or (11) below] in a basis set of
cubic B splines
29
and are folded with an experimental line
shape. This model uses a Gaussian line shape with a FWHM
of 38 meV. Any transition with a Franck-Condon intensity
less than 1 % of the (0,0) transition is discarded.
In these simulations, we adopt for the geometry of the
CH
2
N neutral that favored by Jacox, the GVB-CI ab initio
structure of Bair and Dunning:
19
r
CH
= 1.106 A,
RCN = 1.268 A and 0
HCH
= 118. The neutral frequencies
V
2
(1725 cm - I) and V3 (1337 cm - I) are the matrix IR val-
ues of Jacox.
20
The hot band a fixes the anion H-C-H scis-
soring frequency at V3 a.:: 1400 cm - I. Adjustable parameters
in our fit are the CH
2
N - geometry elements, the C-H sym-
metric stretch frequency (v I ) of the neutral and the vibra-
tional temperature.
Figure 3 displays the Franck-Condon factors expected
from excitation of the eN stretch, v
1
We employ harmonic
J. Chern. Phys . Vol. 94. No.5. 1 March 1991
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3522 Cowles 91 a/.: Photoelectron spectroscopy of CH
2
N-
800 -
400 -
200 -
CH2N
MfZ = 28
Laser "'0 = 488 nm (2.540 e V)
Franck-Condon simulation
using v2 with T vib = 800 K
D
C
"





B

I


A


F


E' : I
): 1'..1 . a
..... y , .. -

I I I I I I I
1.2 1.4 1.6 1.8 2.0 2.2 2.4
CM PHOTOELECTRON KINETIC ENERGY (eV)
FIG. 3. Franck-Condon simulation of the photoelectron spectrum of CH
2
N - using only the C=N stretching mode (v
2
).
potentials for both the ion and the neutral; hence the vibra-
tional functions for these modes, tPlf (Q2) and tPv (Q2)' are
eigenfunctions of a linear oscillator:
+-l-wiQi.

(10)
In expression (10), P2 and Q2 are the momentum operator
and the C N stretch coordinate, W
2
is the C N harmonic
frequency and ti2 is the effective inverse mass, expressed as
an elementl of the G matrix. It seems evident from Fig. 3
that the C N stretch mode is nearly inactive and contrib-
utes very little to the photodetachment spectrum of
CH
2
N - . The C=N bond length of the CH
2
N - ion must be
very close to that ofthe CH
2
N radical. 31
In Fig. 4, we simulate the data using all the symmetric
(a
l
) modes VI' v
2
and V
3
As with V
2
, the scissoring mode
(v
3
) is also well represented by a simple harmonic oscillator.
However, since we have extracted a value for the C-H bond
dissociation energy ofCH
2
N (vida infra) that is unusually
low, Dg (H-CHN) = 23 6 kcallmol, the C-H oscillators
live in a shallow well. Therefore we must use an anharmonic
potential to accurately model the symmetric C-H stretching
mode (VI)' It is convenient to represent this mode in both
the radical and the ion with a Morse oscillator where the
frequencies Wtl = 2860 cm -I and xii = 20 cm -I provide
the best fit to our data:
(11 )
The fit (solid curve) to our experimental spectrum (points)
in Fig. 4 is quite reasonable.
Within the Bom-Oppenheimer approximation, the
same geometry that is used to fit the CH
2
N - spectrum must
also fit the CD
2
N - spectrum. A very important test of our
model is that it properly account for all of the CD
2
N - isoto-
pic shifts observed in Fig. 2. The CD
2
N frequencies must be
related to those ofCH
2
N by the G matrix elements appropri-
ate for VI , V
2
and V
3
The predicted Franck-Condon profile
is displayed with the CD
2
N - data in Fig. 5. We believe the
results of our model are quite reasonable since all of the fre-
quency shifts are faithfully reproduced, however the intensi-
ties of the peaks are not exact. It should be emphasized that
our CD
2
N - experimental spectrum is at a very low S / N. We
were never able to produce intense ion beams (only 75 pAl
of CD
2
N- from CD3N3 although our CH
2
N- currents
(300 pA) were quite acceptable.
Since we can fit both the CH
2
N - and the CD
2
N - spec-
tra with one model, we believe that our simple Franck-Con-
don picture based on three uncoupled oscillators is a plausi-
ble representation for our photodetachment spectra. The
J. Chern. Phys., Vol. 94, No.5, 1 March 1991
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Cowles et al.: Photoelectron spectroscopy of CH
2
N- 3523
800
fIl
~
600
0
t,)
Z
0
~
t>
400
~
Il.:/
0
b
:I:
ll.t
200
MIZ = 28
Laser 1..:: 488 nm (2.540 eV)
Franck-Condon simulation
using VI. v2. and v3 with
T vib = 800 Ji(
(0,0)
1.2 1.4 1.6 1.8 2.0 2.2 2.4
CM PHOTOELECTRON KINETIC ENERGY (eV)
FIG. 4. Franck-Condon simulation of the photoelectron spectrum of CH
2
N - using all of the totally symmetric modes: VI' V
2
and V
3

final geometries and frequencies chosen are summarized in
Table III.
B. Ab Initio calculations
A series of ab initio calculations was carried out on the
CH
2
N radical and CH
2
N - anion to gain insight into the
electronic structures of these species and so to illuminate our
experimental findings. We use the GAUSSIAN 86 package of
computational programs
32
with a standard Gaussian basis
set augmented with polarization and diffuse functions, the 6-
31 + + G** basis.
Several ab initio studies of the CH
2
N radical
19

33
and
one of the anion IS have been reported. In a detailed analysis
of the reaction pathways for H + HCN, Bair and Dunning
l9
determined the electronic structure of the CH
2
N adduct and
the corresponding transition state. These studies were based
on GVB-CI wave functions calculated in a large Gaussian
basis set. Equilibrium geometries and harmonic vibrational
frequencies were reported for CH
2
N and its isomers. Their
CH
2
N GVB-CI geometry was verified by Jacox
20
in her nor-
mal coordinate study and adopted by us in our Franck-Con-
don analysis of the photodetachment of CH
2
N - .
We treated the ion with a Hartree-Fock (RHF) wave
function in a 6-31 + + G** basis set and calculated the har-
monic frequencies at the predicted equilibrium geometry.
Our findings reproduce the results reported earlier. IS Our
RHF calculations approximate the anion wave function as a
simple antisymmetrized product of doubly occupied orbi-
tals. In the expression below the antisymmetrizer or deter-
minant operator is written as d.
'l'eA
I
) = d{lai2aiJai4ai Sai Ib b ~ Ib n. (12)
The calculated ion geometry and frequencies are summar-
ized in Table IV.
For the CH
2
N radical, a Hartree-Fock (UHF)
6-31 + + G** calculation was initially performed and gave
surprising results (see Table IV). Notice that the UHF cal-
culation predicts a substantially longer C N bond length
for CH
2
N than was determined for CH
2
N - in the RHF
computation, an obvious contradiction of the experimental
photodetachment spectra (Figs. 1 and 2) which clearly
show no excitation of the C=N stretch, v
2
Furthermore,
when we compare the UHF {i)'S to the experimental frequen-
cies of Table I, a curiously low value for {i)2 is observed.
Specifically, it is a common finding
34
that when compared
with experiment, the harmonic frequencies of HF calcula-
tions are too high by about 10%. This trend is observed in all
the calculated frequencies save {i)2' the C N stretch.
Whereas {i)3 through {i)6 are too large by 6% to 16%, the
J. Chern. Phys., Vol. 94, No.5, 1 March 1991
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3524 Cowles et al: Photoelectron spectroscopy of CH
2
N-
150
100
50
o
CDZN
MIZ = 30
Laser A.., = 488 run (2.540 eV)
Franck-Condon simulation
using vI. vz. and v3 with
TYib = 800 K
(0.0)
I .
. "..... .
.,
........ -.J ..
. . ..... ' .
1.2 1.4 1.6 1.8 2.0 2.2 2.4
CM PHOTOELECTRON KINETIC ENERGY (eV)
FIG. 5. Franck-Condon simulation of the photoelectron spectrum of CO
2
N - using all of the totally symmetric modes: VI' V
2
and v,.
UHF value of Ct)2 (1631 cm - 1) is actually lower than the
experimental value
20
of 1725.4 cm - 1 (by 6%). We expected
the UHF Ct)2 to be about 1900 cm - 1.
We believe that these anomalous results stem from a
spin-contamination problem inherent to the UHF meth-
od.
35
Since the a and /3 orbitals are permitted to vary inde-
pendently in a UHF calculation, it is well known that they
polarize each other.
36
We find that our UHF vectors for
CH
2
N are badly spin-contaminated with (S2)UHF equal to
0.981 rather than the exact value of l. Our UHF wave func-
tion (which should be a doublet) evidently mixes strongly
with a quartet state. The pair of states to consider is depicted
below:
H*
..
H


(13)
The essential feature of the 2'11 (B
2
) state is that it is a singlet-
coupled 1T electron pair (1T (1T, ) combined with the u orbital
(b
2
) electron as an overall doublet. This state might be rep-
resented as follows:
1
2
'11(B
2
= .if{ Ib n
x (1T(1T,u)(a/3-/3a)a}. (14)
The UHF method mixes this 12'11 (B
2
doublet state with
the 14'11 (B
2
) ) quartet state in which the ( 1T (1T, ) electron pair
is now triplet-coupled and joined with the u(b
2
) electron.
14'11 (B
2
= .if {[ Ib ]
x (1T(1T,u)(a/3+/3a)a}. (15)
It seems plausible that the UHF method might blend some of
the character of the 14'11 (B
2
) ) state into the 12'11 (B
2
) ) func-
tion. Expression (13) suggests that such a mixing would
lengthen the C N bond and lower the vibrational frequen-
cy, as was found (Table IV).
To explore a possible connection between (S2) and the
harmonic frequencies, we then carried out a restricted, open
shell Hartree-Fock (ROHF) 6-31 + + G** calculation on
the CH
2
N radical. This computation constrains all of the
doubly occupied a and /3 orbitals to be identical and forces
(S2) to be the required i. Naturally these additional restric-
tions raise the energy of '11 ROHF above that of '11 UHF' The
ROHF calculated structure for the CH
2
N radical differs
with the UHF geometry (see Table IV) and is about 10
mhartree higher in total energy. The C N bond length
J. Chern. Phys., Vol. 94, No.5, 1 March 1991
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Cowles e/ al.: Photoelectron spectroscopy of CH
2
N-
TABLE IV. Ab initio calculations in a 6-31 + + G** basis.
H
"Z082 A
119 C=N
/1.239 A
H
_
109 C=N
1.240 A
XeB,) XeB,) X('A,)
E(UHF) = - 93.439 558 hartree E(ROHF) = - 93.429 299 hartree E(RHF) = - 93.395 863 hartree
A = 9.628 cm - ,
B = 1.287 cm - ,
C= 1.135cm-
1
Ji.o = 2.52 Debye
A
117 C=N
/1.223 A
H _
xeB, )
A = 9.642 cm - ,
B = 1.328 cm - ,
C= 1.167cm-
1
Ji.o = 2.64 Debye
A = 9.955 cm - ,
B = 1.279 cm - ,
C = 1.133 cm - I
_
108 C=N
1.256 A
X('A, )
E(UMP2) = - 93.701783 hartre.e
A = 9.614cm-
1
E(RMP2) = - 93.720 564 hartree
A=9.872cm-
1
B= 1.352cm-
1
C= 1.185 em-'
Ji.o = 2.54 Debye
Mode
(z), (CH, sym. stretch) a,
(z), (C=N stretch) a,
(z)3 (CH, scissors) a,
(z). (CH, umbrella) b,
(z)s (CH, asym. str.) b,
(z). (CH, rock) b,
Harmonic vibrational modes (cm - ')
CH,NXeB,)
B = 1.240 cm - ,
C= 1.102cm-'
(UHF) (ROHF) (UMP2) (GVB-CI) (Ref. 19) (RHF) (RMP2)
3210 3238 3118 3031 2772 2594
1631 1896 2080 1722 1765 1699
1431 1526 1454 1407 1623 1544
1041 1152 1170 1012 1089 1058
3299 3328 3199 3098 2600 2332
1066 1080 976 1007 1265 1171
TABLE V. Thermochemical values (kcal mol-I).
Quantity
EA(CH,N)
EA(CD,N)
IP(CH,N)
IP(CD,N)
All';,,'d (CH, N-H)
aHJ(CH,NH)

aHJ(CH,N - )
aHJ(CH,N+ )
aHJ(HCNH +)
D(CH,N-H)
D(H-HCN)
D(H,C=N)
D(H,C=NH)
D(H,C=O)
OK
11.8 0.2
11.5 0.2
386 5
28.3 3.2
61 6
50 6
228 3
85 5
23 6
144 6
ISO 3
177.8 0.6
298K Derivation
Electron affinities & ionization potentials
11.8 0.2 photodetachment spectroscopy
photodetachment spectroscopy
217 2 photoionization spectroscopy
217 2 photoionization spectroscopy
Gas phase acidity
388 5 proton transfer kinetics
Heats of formation
26.4 3.2 hydride transfer kinetics
606 D(CH,N-H) - aH/(H) + aH/(CH,NH)
496 aH/(CH,N) - EA(CH,N)
277 6 IP(CH,N) + All/(CH,N)
227 3 aH/(HCN) + aH/(H + ) - PA(HCN)
Bond dissociation energies
86 5 aH,dd (CH,N-H) + EA(CH,N)-IP(H)
24 6 All/(HCN) + aH/(H) - aH/(CH,N)
145 6 All/(CH,) + All/(N) - aH/(CH, N)
152 3 aH/(CH,) + All/(NH) - aH/(CH,NH)
179.4 0.6 aH/(CH,) + All/(O) - aH/(CH,O)
Isomerization energy
- 51 7 aH/(HCNH+) - aH/(H,CN+)
Auxiliary values (Ref. 48)
3525
Reference
This work
This work
17
17
14
16
PA
300
(HCN) = 171.42 (Ref. 49); aHJo(CH,) =92.80.6 (Ref. 50); aHJo(NH) = 85.40.3 (Ref. 51); aHJo(CH,O) = -26.00.1 (Ref.
52); aHJo (HCN) = 32.4 2, (H) = 51.6336 0.0014; aHJo (0) = 58.984 0.024; (N) = 112.53 0.024; aHJo (H +)
= 365.221 0.009, aHJo (H - ) := 34.242 0.005
J. Chern. Phys., Vol. 94, No.5, 1 March 1991
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3526 Cowles fiJt a/.: Photoelectron spectroscopy of CH
2
N-
(1.239 A) is now nearly identical to that of the RHF ion
(1.240 A), in good agreement with our experimental find-
ings which indicate that oRcN ,0.02 A. Several of the
ROHF {w} values are similar to the UHF {w} results except
for W
2
which is now 1896 cm - I. In summary, we believe that
the ROHF calculation better represents the CH
2
N radical
since the computed harmonic frequencies are roughly 10%
higher than the experimental values and the C N bond
lengths are comparable in the ion and neutral.
The contribution of electron correlation to the potential
energy surface is certain to be large. We attempt to quantify
this important effect via perturbation methods by applica-
tion of the second-order MQSller-Plesset correction, (MP2).
Table IV shows that when we reoptimize the CH
2
N - RHF
geometry, the C-H bond lengthens to 1.139 A and the C N
bond grows to 1.256 A; the total energy of the ion falls by
0.325 hartree, about 8.8 eV! This post Hartree-Fock treat-
ment also leads to important changes in methylene amido-
gen; reoptimization of the UHF CH
2
N geometry leads to a
serious shortening of the C N bond length from 1.260 to
1.223 A in the UMP2 radical. The energy of the fully relaxed
UMP2 CH
2
N radical falls by 0.262 hartree (7.1 e V). At this
level of computation, CH
2
N - is now bound with respect to
the CH
2
N radical by 18. 78 mhartree (0.5 e V or 12 kcall
mol). The contraction of the C N bond in the UMP2 radi-
cal is attended by a dramatic rise in the vibrational frequency
as W
2
goes from 1631 to 2080 cm - I. The charge distribution
in CH
2
N does not seem to vary much; the dipole moment,
flD' only changes slightly (2.52 D --+ 2.54 D) as one incorpo-
rates correlation.
We are disappointed with the results of these "stan-
dard" ab initio computations. The vibrational frequencies
tabulated in Table IV are only an imperfect match to the
experimental findings of Tables I and III. The unrestricted
Hartree-Fock method necessarily produces a spin-contami-
nated wave function which leads to an incorrect C N bond
length and a faulty C=N vibrational frequency; both RCN
and W
2
are too small. All attempts' to remedy this UHF fail-
ure by perturbation methods (Mfi) were unsuccessful. One
should use a projected MP2 method with full geometry opti-
mization 37 to attack this problem but our set of routine com-
puter codes does not include this option. Likewise we could
not pursue a MQSller-Plesset correction to the ROHF vec-
tors. We conclude that the radical geometry and harmonic
frequencies from the GVB-CI method are superior to our
Hartree-Fock and second-order MQSller-Plesset results.
c. Thermochemistry
We can make use of the electron affinity of CH
2
Nand
its recently measured ionization potential to extract some
important thermochemical values; these findings are collect-
ed together in Table V. It is interesting to note that CH
2
N is
isoelectronic with vinyl4 radical, CH
2
CH, and that the elec-
tron affinities are comparable:
H, A
, V 0.511 0.008 eV
C==N ..... ---
H/
(16)
0.667 0.024 eV

The ionization process for the CH
2
Nand CH
2
CH radicals
will be more complicated since the resulting cations rear-
range extensively. Photoionization
38
of vinyl radical leads to
a bridged
39
cation, C
2
H3+; the observed spectrum is very
complicated with IP(CH
2
CH) = 8.59 0.03 eV which
contrasts with that of methylene amidogen,
IP(CH
2
N) = 9.4 0.1 eV.
Use of Eq. (2) enables one to find the N-H bond
strength of methyleneimine as Dg (CH2N-H) = 85 5
kcallmol.
8S S
XIA' X
2
B
2
(18)
The heat of formation of CH
2
NH has been established from
the bracketing studies described in Eq. (6). Therefore use of
the dissociation energy from Eq. (18) yields the heat of for-
mation of the radical CH
2
N. Then we can use the heat of
formation of HCN to extract the C-H bond strength of
methylene amidogen, Dg (H-CHN) = 23 6 kcallmol.
H",
/C==N --.... - H-C=N
H X2B2 X Il;+
23 6
+H. (19)
This very weak C-H bond is reminiscent of that in formyl
radical, H-CO, and the vinyl radical /3 C-H bond. In the
earlier GVB-CI studyl9 of the addition ofH atom to HCN,
Dg (H-CHN) was estimated to be 19 kcallmol, a value
compatible with Eq. (19).
Prior to deriving the double-bond energies for CH
2
==0,
CH
2
=NH and CH
2
=N in Table V, we guessed that quan-
tum mechanical "exchange stabilization" might be mani-
fested
40
in these values. Specifically, rupture of the double
bond generates CH
2
in each case but CH
2
N also produces
(4S)N atoms.
144 6
+
(20)
Thus, while the dissociation energies for the isoelectronic
species CH
2
==0 and CH
2
=NH should be comparable,
the exchange stabilization associated with the high spin
N atoms should lead to a lower dissociation energy for
CH
2
=N. We find
41
Dg (CH
2
==O) = 177.8 0.6 kcal-
/mol, Dg (CH
2
=NH) = 150 3 kcal/mol and
Dg (CH
2
-N) = 144 6 kcal/mol. Admittedly, more
striking examples of exchange stabilization have been docu-
mented.
42
Finally we can use our heat of formation for CH
2
N with
the recent measurement ofIP (CH
2
N) to glean some insight
into the rearrangement energetics of the isomeric cations,
CH
2
N+ and HCNH+. From Table V, !:JIJ298 (CH
2
N+)
is 277 6 kcallmol while proton affinity studies of HCN
have fixed !:JIJ298 (HCNH +) as 227 3 kcallmol. Thus
we have an estimate for the isomerization energy of
J. Chem. Phys., Vol. 94, No.5, 1 March 1991
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Cowles et al.: Photoelectron spectroscopy of CH
2
N- 3527
(21)
The linear HCNH + ion is thought
43
to be a major determi-
nant of interstellar [HCN]/[HNC] ratios and has been de-
tected in the laboratory44 and in interstellar clouds.
45
Theo-
retical studies predict
46
that the C
2v
isomer, CH
2
N +, is
unstable with respect to isomerization to the linear ion. A
careful search of the energy gradients about the C
2v
geome-
try reveals no barrier between CH
2
N + and HCNH + . The
most recent estimate
47
of the energy difference between the
C
zv
and C
oov
structures is 74 kcallmol. However, note that
synchrotron experiments which ionize CH
2
N produce a
CH
2
N + ion with the geometry of the radical so that our
estimate of 51 kcallmol can only be loosely compared to
these ab initio results.
ACKNOWLEDGMENTS
We would like to thank Dr. R. Bruce Klemm (BNL)
and Dr. Louis J. Stief (NASA) for preliminary communica-
tion of the CH
2
N ionization potential. We are also indebted
to Dr. Bill Kirchoff (DOE Chemical Physics) for alerting us
to the importance of these synchrotron measurements of the
CH
2
N IP. We have also benefited from discussions about
spin-contaminated UHF and UMP2 wave functions with
Dr. Mark S. Gordon (NSF). This work was supported by a
grant from the Chemical Physics Program, United States
Department of Energy (DE-FG02-87ERI3695). The elec-
tronic structure and Franck--Condon calculations were car-
ried out on a J.l V AX acquired with the help of the National
Science Foundation (CHE-8407084).
I c. R. Moylan and J. I. Brauman, Annu. Rev. Phys. Chern. 34, 187
(1983).
2 Ionization potentials and electron affinities are adiabatic enthalpy
changes strictly defined at 0 K, while and commonly repre-
sent changes of enthalpy at 298 K. Equation (2) is more properly written
as
(R-H) = (R-H) + EA(R) - IP(H) -
The difference in the integrated heat capacities can be written in the fol-
lowing manner: -1- m
98
+ 1) [H + 1 - (1) [H In the absence of low-lying elec-
tronic states, the heat capacity correction is generally less than 0.5 kcall
mol since the structures and vibrational frequencies of the ions and neu-
trals are similar. Because the unC(,rtainties of the measurements
are commonly 2 kcallmol or greater, this correction is usually ignored;
thus ... 0 kcallmol. (See Ref. 3, Sec. 3.3.) We adopt theconven-
tion that C
p
(e - ) =0. In Table V we have explicitly applied the heat ca-
pacity correction to obtain proper Dg (R-H) and (R-H) values.
3S. G. Lias, J. E. Bartmess, J. F. Lil:bman, J. L. Holmes, R. D. Levin, and
W. G. Mallard, Gas-Phase Ion al/d Neutral Thermochemistry, J. Phys.
Chern. Reference Data 17, Supplement No. I (1988).
4K. M. Ervin, S. Gronert, S. E. Barlow, M. K. Gilles, A. G. Harrison, V.
M. Bierbaum, C. H. DePuy, W. C. Lineberger, and G. B. Ellison, J. Am.
Chern. Soc. 112, 5750 (1990).
5 The proton affinity of the ion is identical to the gas phase acidity of the
neutral; thus PA(CH
2
N -) (CH
2
N-H).
6G. Marston, F. L. Nesbitt, D. F. Nava, W. A. Payne, and L. J. Stief, J.
Phys. Chern. 93, 5769 (\989).
7 G. Marston, F. L. Nesbitt, and L.J. Stief,J. Chern. Phys. 91,3483 (1989).
8 C. U. Morgan and R. A. Beyer, Combust. Flame 36, 99 ( 1979); X. Zhao,
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(1975).
13 D. W. Turner, C. Baker, A. D. Baker, and C. R. Brundle, Molecular Pho-
toelectron Spectroscopy (Wiley, New York, 1970), Chap. 5.
14S. R. Kass and C. H. DePuy, J. Org. Chern. 50, 2874 (1985).
I, Unpublished studies by Dr. H. Benton Ellis, Jr. (University of Colorado,
1983).
16D. J. DeFrees and W. J. Hehre, J. Phys. Chern. 82,391 (1978).
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27 The value of y is established by study of the photoelectron spectra of the
tungsten atom. Detachment of the W - ion produces several states ofW Ij
one can detect W[a
5
D(J=0)J-W-, W[a'D(J= I)J-W-,
W[a'D(J=2)J-W-, W[a
5
D(J=3)J_W-, W[a'
6
D(J=4)J
- W-, as well as W[a
7
S(J = 3) J- W-. These intervals have beenestab-
lished by atomic spectroscopy and are tabulated by Charlotte E. Moore,
Atomic Energy Levels, Vol. II, NSRDS-NBS 35 (US GPO, Washington,
DC, 1971). Use of these precisely known intervals fixes y.
28 P. C. Engelking, J. Phys. Chern. 90, 4544 ( 1986).
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(McGraw Hill, New York, 1955). Appendix VI, pp. 303-306. We use the
following expressions in which 9 is the H-C-H angle and the C-H bond
length is r; the reciprocal masses for C and H are written as
f-lH == (mass hydrogen) - I and f-lc == (mass carbon) - I; til = /lH
+ /lc (1 + cos 9), = /lc + /IN' ti3 = 2/lH/r + 2/lcl
r(l-cos9).
31 From our modeling of the CH
2
N - and CD
2
N - spectra, we believe that
ORCN cannot exceed 0.02 A. Consequently RCN (CH
2
N) = 1.268 A
implies that RCN (CH
2
N - ) = 1.27 0.02 A.
32 GAUSSIAN 86, M. J. Frisch,J. S. Binkley, H. B. Schlegel, K. Raghavachari,
C. F. Melius, R. L. Martin, J. J. P. Steward, F. W. Bobrowicz, C. M.
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Fox, E. M. Fleuder, and J. A. Pople, Carnegie-Mellon University, Pitts-
burgh, P A, 1986.
33G. F. Adams, D. R. Yarkony, R. J. Bartlett, and G. D. Purvis, Int. J.
Quantum Chern. 23, 437 ( 1983).
34 J. A. Pople, H. B. Schlegel, R. Krishnan, D. J. DeFrees, J. S. Binkley, M.
J. Frisch, R. A. Whiteside, R. F. Hout, Jr., and W. J. Hehre, Int. J. Quan-
tum Chern. Symp. 15, 269 (1981); D. J. DeFrees and A. D. McLean, J.
Chern. Phys. 82, 333 (1985); B. A. Hess, Jr., L. J. Schaad, P. Carsky, and
R. Zahradnik, Chern. Rev. 86, 709 (1986).
35 P. M. W. Gill, J. A. Pople, L. Radom, and R. H. Nobes, J. Chern. Phys.
89,7307 (1988).
36 A. Szabo and N. S. Ostlund, Modern Quantum Chemistry: Introduction to
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3528
Cowles et a/.: Photoelectron spectroscopy of CH
2
N-
41 It is also pertinent to recall that Dg (CH
2
=CH
2
) = 171.0 1.2 kcaI!
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J. Chern. Phys., Vol. 94. No.5. 1 March 1991 This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.72.2.27 On: Wed, 06 Nov 2013 05:07:31