JOURNAL OF CHEMICAL PHYSICS VOLUME 115, NUMBER 15 15 OCTOBER 2001

Gas phase electronic spectrum of C3H in the visible

H. Ding, T. Pino, F. Güthe, and J. P. Maier
Institute for Physical Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056, Basel, Switzerland
共Received 27 June 2001; accepted 30 July 2001兲
The electronic spectrum of C3H has been observed by means of a resonant two color two photon
ionization technique sampling a supersonic plasma source. On the basis of ab initio calculations,
vibrational and rotational analysis, the complex vibronic system observed in the visible and near UV
is assigned to three electronic transitions, Ã 2 A ⬘ ←X 2 ⌸, B̃ 2 A ⬙ ←X 2 ⌸ and C̃ 2 A ⬙ ←X 2 ⌸ of C3H.
Potential curves along the CCH bending coordinate have been obtained because of its role for the
electronic spectrum and dynamics of C3H. © 2001 American Institute of Physics.
关DOI: 10.1063/1.1404391兴

I. INTRODUCTION spectroscopy in a molecular beam. Theoretical calculations

The C3H radical is among a number of carbon contain-
ing molecules such as HC2n⫹1 N, (n⫽1 – 5), Cn H, (n
⫽2 – 6) and Cn N, (n⫽3) which have been detected in the
interstellar medium 共ISM兲.1,2 It is considered a key molecule
in the carbon-chain growth in the ISM.3,4 Both isomers of
C3H, the linear (l-C3H) and cyclic (c-C3H), have been
identified in the ISM by means of radioastronomy.5–7 Reac-
tion models based on radiative association, dissociative re-
combination and exothermic ion-molecule processes were
used to simulate observed densities but failed to reproduce
the ratio of the linear to cyclic C3H isomers.3,8 –11 Fast
neutral–neutral reactions are helpful in understanding the
formation of the two isomers.12–14 In order to extend the
possibility of their detection in different regions of the ISM,
the electronic spectra in the gas phase are required.
C3H is a well-studied molecule in its ground state. Ac-
cording to ab initio calculations, c-C3H is energetically more
stable than l-C3H by 9–13 kJ/mol.11,13,15,16 The c-C3H has a
2
B 2 ground state and the calculated geometry is in agreement
with microwave studies.6,11,13,15–18 Its structure is shown to
be Jahn–Teller distorted due to a close lying 2 A 1 excited
state 共1.2 eV兲.6,17,18 Other electronic excited states of c-C3H
were predicted to lie in the UV.16,19 Microwave spectroscopy
on l-C3H has shown that the ground state is 2 ⌸. 20–23 Theo-
retical studies on the structure of l-C3H have been carried
out and the molecule is calculated to be linear or quasi-linear
in its X 2 ⌸( 2 A ⬘ ) ground state.24,11,13,15 The barrier to linear-
ity is calculated to be small (100– 200 cm⫺1) and the upper
component 2 A ⬙ remains linear according to ab initio
results.11 The calculated vibrational frequencies are in
agreement11,15 with the infrared spectra measured in cryo-
genic matrices.25–27 Electronic excited states of l-C3H were
predicted to lie in the UV. These are the 2 ⌬, 2 ⌺ ⫹ and 2 ⌺ ⫺
states19 as found for the isoelectronic molecules C⫺
29 30
CNC and CCN. All of these show evidence of Renner–
Teller interaction in both the ground and the first excited
electronic states.
In this article the visible and near-UV electronic spec-
trum of C3H and C3D have been detected for the first time by
mass-selective resonant two color two photon ionization
were carried out in order to guide the assignment and to
investigate the geometrical changes.
II. EXPERIMENT
The experimental setup has been described previously.31
Briefly it consists of a molecular beam combined with a
linear time of flight 共TOF兲 mass-analyzer and the source
used to produce C3H is a pulsed valve coupled to an electric
discharge. A gas mixture of 0.3% of acetylene or
d 2 -acetylene in Ar or He 共backing pressure ⬃8 bar兲 is ex-
panded through a ceramic body which holds two steel elec-
trodes separated by a ceramic spacer of a few mm. A high
voltage pulse 共600–900 V; 100 ␮s兲 is applied between the
electrodes from a pulse generator. All initially formed ions
are removed from the beam by an electric field perpendicular
to the molecular beam behind the skimmer before entering
the extraction zone of the TOF. The neutral molecules are
then photoionized and accelerated toward the MCP-detector.
The resonant two color two photon ionization 共R2C2PI兲
spectrum has been recorded in the 330–570 nm range. Exci-
tation photons were delivered from a dye-laser 共⬃0.1 cm⫺1
bandwidth兲 pumped by a XeCl excimer laser. The pulse
energy was typically between 10 and 20 mJ. The intensity of
the dye-laser was monitored by a photodiode. The spectra
were divided by the dye curves for normalization. The
ionizing photons were delivered by a F2 excimer laser 共157
nm兲, its beam path being flushed continuously with N2. The
dye-laser beam was anti-collinear with the molecular beam
while the excimer laser beam was perpendicular, allowing a
maximum overlap.
III. RESULTS
3,
28
The R2C2PI spectra of C3H and C3D are shown in Fig.
1. The spectra appear to be congested and irregular espe-
cially for C3D although the molecules sampled are at low
temperature. A large change of geometry is indicated by the
Franck–Condon profile of the observed vibrational progres-
sion 共Fig. 2兲. Deuteration indicates that the progression in-
volves the CCH bending mode and the difference between

0021-9606/2001/115(15)/6913/7/$18.00 6913 © 2001 American Institute of Physics

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6914 J. Chem. Phys., Vol. 115, No. 15, 15 October 2001 Ding et al.

TABLE I. Bands observed in the gas phase electronic spectrum of C3H

measured by R2C2PI and the vibrational assignment.

Label ␭共nm兲 ␯ (cm⫺1) ⌬ ␯ (cm⫺1) Assignment Intensity

à 2 A ⬘ ←X̃ 2 ⌸ 1/2
1 521.04 19187 0 0 00 (K⫽0←1) mw
2 518.98 19263 76 0 00 (K⫽2←1) mw
3 498.16 20 068.3 881.3 4 10 (K⫽0←1) m
4 496.08 20 152.4 965.4 4 10 (K⫽2←1) m
5 493.17 20 271.3 1084.3 3 10 (K⫽0←1) w
6 491.33 20 347 1160 3 10 (K⫽2←1) w
7 487.0 20 528.1 1341.1 5 10 4 10 (K⫽0←1) m
9
再 冎再485.6
484.4
20 587.3
20 638.3 冎 再 1400.3
1451.3 冎再 5 10 4 10 共 K⫽2←1 兲
5 30 共 K⫽2←1 兲 冎 m

11 478.32 20 900.8 1713.8 4 20 (K⫽0←1) s

12 476.31 20 988.6 1801.6 4 20 (K⫽2←1) s
475.52 21 023.7 1836.7 2 10 (K⫽0←1)
FIG. 1. Electronic spectra of C3H and C3D in the gas phase recorded by a 473.8 21 100 1913 2 10 (K⫽2←1)
resonant two photon two color ionization approach. 14 472.48 21 159 1972 3 10 4 10 (K⫽0←1) mw
16 470.57 21 245 2058 3 10 4 10 (K⫽2←1) mw
18 467.88 21 367.2 2180.2 5 10 4 20 (K⫽0←1) m
the C3H and C3D spectra is a signature of strong vibronic 20 464.2 21 536.4 2349.4 5 10 4 20 (K⫽2←1) m
coupling. The characteristics of the vibronic bands in the 21 461.04 21 684 2497 4 30 (K⫽0←1) s
spectrum of C3H are given in Table I.
The vibronic bands do not show rotationally resolved
22
再 460.4
458.61 冎再 21 714.2
21 799 冎 再 2527.2
2612 冎 再 4 30 共 K⫽2←1 兲
— 冎 s

23 454.69 21 987 2800 1 10 (K⫽0←1)? s

structure. Spectra recorded in absorption by a cavity ring 25 445.8 22 425 3238 4 40 (K⫽0←1) ms
down technique exhibit the same profiles,32 indicating intrin-
sic lifetime broadening. The FWHM of the vibronic bands B̃ 2 A ⬙ ←X̃ 2 ⌸ 1/2
lying in the red part of the spectrum is ⬃10 cm⫺1 increasing 8 486.77 20 538 0 0 00 (K⫽0←1) m
to ⬃30 cm⫺1 to the blue, implying individual rotational line- 10 482.68 20 711.9 173.9 0 00 (K⫽2←1) mw
widths ⲏ4 cm⫺1. Therefore the lifetimes in the excited states 13 475.35 21 031 493 5 10 (K⫽0←1) m
15 471.32 21 211 673 5 10 (K⫽2←1) mw
are on the sub-ps time scale suggesting fast intramolecular 17 468.88 21 321.5 783.5 4 10 (K⫽0←1) ms
dynamics. It is remarkable that the recording of the R2P2CI 19 464.96 21 501 963 4 10 (K⫽2←1) ms
spectrum with ns lasers is possible although the lifetime is on 24 454.0 22 021 1483 4 20 (K⫽0←1) s
the sub-ps time scale.
The vibronic system of C3H can be divided into two C̃ 2 A ⬙ ←X̃ 2 ⌸ 1/2
parts. The red one (19 000– 23 000 cm⫺1) is composed of 431.45 23 171 0 0 00 (K⫽0←1) vs
424.96 23 525 354 — vs
relatively sharp peaks and an assignment is carried out in this
region. The spectral congestion is a signature of a strong
mixing between at least two electronic excited states and no On the basis of the following rotational and vibrational
straightforward assignment can be given 共Fig. 2兲. The blue analysis, the vibronic system below 23 000 cm⫺1 is assigned
part (23 000– 27 000 cm⫺1) comprises a number of indi- to two electronic transitions of l-C3H and the upper states
vidual broad peaks. are bent. These are assigned to the two components corre-
lated to the 2 ⌬ state predicted as the first electronic excited
state.19 This assignment is supported by ab initio calculations
共see Sec. IV兲. On the basis of these theoretical studies, other
states above 23 000 cm⫺1 are detected.
IV. THEORETICAL CALCULATIONS
A. Ground states of the two isomers
All ab initio calculations were undertaken using the
MOLPRO package33 with Dunning type basis sets.34 The
ground state geometry of the cyclic conformer was taken
from the literature.11,17,18 Although c-C3H has been shown to
be Jahn–Teller distorted,18 this effect was not considered and
the calculations were carried out in the C 2 v group. The
ab initio geometry for l-C3H ground state has been calcu-
lated to be slightly bent with a rather small barrier to
FIG. 2. Close up of the C3H spectrum below 23 500 cm⫺1, i.e., the region
below the barrier to linearity in the à and B̃ electronic excited states. A
linearity.11,15 The influence of the level of theory and the size
simple numeration is used for the peak labels. A zoom of band 11 is given to of the basis set on the geometry was investigated. At the
show the spin-orbit splitting in the X 2 ⌸ ground state. CASSCF/aug-cc-pVTZ level, full valence calculations pre-

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J. Chem. Phys., Vol. 115, No. 15, 15 October 2001 Electronic spectrum of C3H 6915

TABLE II. Optimized geometry of the l-C3H at different levels of theory and basis set sizes. The bond lengths are in Å, and the angles in degrees. The barrier
to linearity is also given.

CASSCF RCCSD共T兲
Basis set aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ TZP 共Ref. 15兲 cc-pVQZ cc-pVTZ

Energy 共H兲 ⫺114.161 072 ⫺114.185 617 ⫺114.199 244 2 ⫺114.456 072 ⫺114.456 263 76 ⫺114.485 59
Barrier (cm⫺1) 156 0 0 83.6 13 0
l(C1–C2) 1.3589 1.3414 1.3634 1.336 1.345 1.3437
l(C2–C3) 1.2755 1.2496 1.2513 1.253 1.251 1.2447
l(H–C3) 1.066 1.0541 1.0758 1.072 1.067 1.0655
⌰共H–C1–C2兲 158.3 180.0 180.0 156.5 165.67 180.0
⌰共C1–C2–C3兲 174.1 180.0 180.0 174.0 176.43 180.0

dict a linear equilibrium geometry 共Table II兲. A bent geom-
etry is found if only part of the valence electrons are in-
cluded in the active space because of an unbalanced
description between the CvCvCH and C–CwCH reso-
nance structures. The use of larger basis sets tends to correct
this behavior. At the restricted CCSD共T兲 level,35 again the
size of the basis set is crucial. Ochsenfeld et al. predict a
bent structure, while their single point calculations with
larger basis sets tend to favor the linear one.15 In the present
study the calculations show that the structure tends to the
linear geometry with increasing size of the basis set 共Table
II兲. Thus the ground state of l-C3H is linear and dominated
by the C–CwCH resonance structure.
B. c -C3H excited states
in the 2 A 1 state, C2 –C3⬃1.51 Å). The second electronic ex-
cited state is predicted to be a 2 B 1 state. It corresponds to the
promotion of an electron from the (3b 2 ) to the (2b 1 ) orbital
and shows a decrease of the C2 –C3 bond length
(⬃1.265 Å). The adiabatic excitation energy is predicted to
be 2.96 eV. This is close to the dominant vibronic bands
recorded under the present conditions. However, the transi-
tion is dipole-forbidden in the C 2 v group. It is concluded that
the cyclic isomer could only weakly contribute to the present
spectrum due to the Jahn–Teller distortion.
C. l -C3H excited states
l-C3H has a X 2⌸ ground state with
. . . .(6 ␴ ) (1 ␲ ) (7 ␴ ) (2 ␲ ) 1 electronic configuration. The
2 4 2

Calculations were performed at the full valence
CASSCF/aug-cc-pVTZ level, all electronic states being op-
timized simultaneously at a given geometry. Although Jahn–
Teller distorted, c-C3H can be described as having a X 2 B 2
ground state with . . . .(5a 1 ) 2 (1b 1 ) 2 (6a 1 ) 2 (3b 2 ) 1 electronic
configuration 共C 2 v group兲.18 The sensitive coordinate for de-
termining the equilibrium geometry of a given electronic
state is the length of the C2 –C3 bond opposite to the carbon
bound to the hydrogen.19 This comes from the fact that the
(3b 2 ) orbital has (C2 –C3) anti-bonding character.16 The en-
ergetic order of the different states is therefore found to de-
pend on this coordinate and was varied between 1.15 and
1.55 Å. The vertical excitation energies at the ground state
geometry 共C2 –C3⬃1.38 Å, Ref. 18兲 are given in Table III.
The first excited state is 2 A 1 in agreement with previous
work16,18,19 and corresponds to the promotion of an electron
from the (3a 1 ) to the (3b 2 ) orbital 共dominant configuration
(7 ␴ )→(2 ␲ ) excitation leads to 4 ⌺ ⫺ , 2 ⌬, 2 ⌺ ⫺ and 2 ⌺ ⫹
states, while ␲ → ␲ excitation yields 4 ⌸, 2 ⌽, and three 2 ⌸
states. As a first step, vertical electronic excitation energies
were calculated at the ground state geometry. These are ob-
tained at the full valence CASSCF/aug-cc-pVTZ level in the
C 2 v group and compared with previous work along with the
experimental positions of the isoelectronic species 共Table
III兲. As in the spectra of C⫺ 3,
28
CNC29 and CCN30 the lowest
electronic states are dominantly characterized by the
(7 ␴ ) 1 (2 ␲ ) 2 configuration. However, the experimental spec-
trum reveals that bent geometries have to be considered and
the CCH angle is the important coordinate.
The geometries of the first three excited state have been
optimized in the C s group at the CASSCF/aug-cc-pVTZ
level including 11 electrons in 12 a ⬘ and 3 a ⬙ orbitals. The
geometries are given in Table IV and point out that all are
trans-bent. The two states à and B̃, correlated to the 2 ⌬

TABLE III. Calculated vertical excitation energies 共eV兲 at the ground state geometry for the linear and cyclic isomer of C3H, along with the isoelectronic
species.

l-C3H CCN CNC C⫺

3 c-C3H

State CASSCF a
H 共Ref. 19兲
v
Gas phase 共Ref. 30兲 Gas phase 共Ref. 29兲 Gas phase 共Ref. 28兲 State CASSCFa MRCI 共Ref. 16兲 Hv 共Ref. 19兲
2
⌬ 2.962 4.969 2.636 3.762 3.068 2
A1 1.223 1.18 1.418
2 ⫺
⌺ 3.078 5.697 2.779 4.315 3.217 2
B1 3.485 3.34 3.858
2 ⫹
⌺ 3.658 5.219 3.306 2
A2 3.937 3.81 4.578
2
⌸ 3.917 2
B1 4.632 -
2
⌽ 4.815 2
A2 4.94 6.95
2
⌸ 5.33 2
A1 5.155 7.775
2
B2 6.62 8.445
a
This work.

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6916 J. Chem. Phys., Vol. 115, No. 15, 15 October 2001 Ding et al.

TABLE IV. Calculated geometries of l-C3H in the first four electronic states at the CASSCF/aug-cc-pVTZ
level. The bond lengths are in Å, the angles in degrees and the rotational constants in cm⫺1. The adiabatic
excitation energies 共eV兲, along with the oscillator strengths in parenthesis, are also given.

X 2⌸ Ã 2 A ⬘ B̃ 2 A ⬙ C̃ 2 A ⬙

Energy 共eV兲 0 2.05(4.2⫻10⫺3 ) 2.22(7.5⫻10⫺3 ) 2.84(5.6⫻10⫺3 )

l(C1 –C2) 1.3414 1.2460 1.2537 1.2506
l(C2 –C3) 1.2496 1.4056 1.3791 1.3234
l(C3 –H) 1.0541 1.0888 1.0636 1.0792
⌰(C1 –C2 –C3) 180.0 169.7 174.4 173.4
⌰(C2 –C3 –H) 180.0 109.0 137.3 149.6
A - 17.638 39.84 71.4
B 0.3619 0.3734 0.3648 0.377
C - 0.3657 0.3618 0.375

state, are predicted to be strongly bent with a CCH angle of the first two bands 共1,2兲 of the vibrational progression are
109° and 137.3°, respectively. Accordingly the C2 –C3 bond separated by 77 cm⫺1 giving A ⬘ ⬃19.2 cm⫺1. This value im-
length increases upon excitation. At these points, calculations plies a strongly bent geometry and the deduced CCH angle is
including 13 electrons in 12 a ⬘ and 3 a ⬙ orbitals were also about ⬃115° assuming a linear carbon skeleton.
performed for the other states. Based on this analysis, the vibronic band system com-
The calculated adiabatic excitation energies and os- posed of double-peaks shows that the transition moment is
cillator strengths are reported in Table IV. The calculated perpendicular to the top axis and the upper state is strongly
electronic transitions à 2 A ⬘ ←X 2 ⌸, B̃ 2 A ⬙ ←X 2 ⌸ and bent. According to the ab initio calculations this is the 2 A ⬘
C̃ 2 A ⬙ ←X 2 ⌸ have transition moments mainly perpendicular component of the 2 ⌬ state. The calculated A constant
to the top axis. The absolute values increase with the CCH (17 cm⫺1) is in agreement with the experimental one,
bending angle for the two first transitions while decrease for 19.2 cm⫺1. The B̃←X 2 ⌸ electronic transition is to the upper
the third one. The oscillator strengths were estimated by tak- component of the 2 ⌬ state, 2 A ⬙ . In these electronic transi-
ing mean values for the transition moments and are found tions hybrid bands could be observed but the theoretical cal-
below 10⫺2 共Table IV兲. culations show that the perpendicular components dominate.
The profile of the vibronic bands reveals a weak shoul-
V. DISCUSSION
A. Band type analysis
The K-structure provides information on the electronic
excited states even though only rotational profiles of the
bands are apparent. According to the theoretical results the
l-C3H ground state is linear and the dominant vibrational
progression shows that a large change of geometry occurs
upon excitation 共Fig. 2兲. The vibronic system below
23 000 cm⫺1 is due to bent-linear electronic transitions from
the X 2 ⌸ ground state. l-C3H is an asymmetric top but can
be considered close to a prolate symmetric top and the quan-
tum number K of the angular momentum about the top-axis
is well defined. The selection rules are: ⌬K⫽0 for a parallel
band, ⌬K⫽⫾1 for perpendicular bands.
A characteristic feature is the clear double peak sub-
structure of the vibronic bands 共1,2; 3,4; 11,12; 21,22兲 com-
posing the dominant vibrational progression 共Fig. 2兲. It is a
signature of the K-structure. In the ground state only the
electronic and vibrational angular momenta contribute to K ⬙ ,
that is K ⬙ ⫽ 兩 l⫹⌳ 兩 , and ⌳⫽1 (X 2 ⌸ electronic state兲 implies
K ⬙ ⫽1 for the vibrational ground state. For a transition mo-
ment perpendicular to the top-axis two components
K⫽0←1 and K⫽2←1 are expected for the cold molecule
as is observed through the double peak structure. The energy
level diagram of this K-structure is shown in Fig. 3. The two
subbands are separated by the interval between the K ⬘ ⫽0 FIG. 3. Energy diagram illustrating the rotational structure of the
and 2 levels in the upper state, that is 4(A ⬘ ⫺ 21 (B ⬘ ⫹C ⬘ )) Ã 2 A ⬘ ←X 2 ⌸ electronic transition. Only the perpendicular components are
⬃4A ⬘ because A ⬘ ⰇB ⬘ ⬇C ⬘ . The double peaks composing observed in this bent-linear transition.

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J. Chem. Phys., Vol. 115, No. 15, 15 October 2001
TABLE V. Comparison of the vibrational frequencies (cm⫺1) of l⫺C3H in
different electronic states.
X 2⌸ Ã 2 A ⬘ B̃ 2 A ⬙
Ar matrix 共Ref. 26兲 Theory 共Ref. 15兲 Gas phase Gas phasea
a revealing that the barrier to linearity lies within this energy
v 1 (a ⬘ ) 3238 3613 2800
v 2 (a ⬘ ) 1824.7 1925 1836
v 3 (a ⬘ ) 1159.8 1095 1091
v 4 (a ⬘ ) 789 881.3 783.5
v 5 (a ⬘ ) 464 460 493
v 6 (a ⬙ ) 371
a
This work.
der to the red of the peaks, separated by about 14 cm⫺1 共Fig.
2兲. This value is consistent with the spin-orbit splitting in
ground state of l-C3H, 14.2 cm⫺1 共Refs. 20–23兲, as illus-
trated in Fig. 3. The rotational temperature is estimated to be
⬃10 K from the intensity ratio between the 2 ⌸ 1/2 and 2 ⌸ 3/2
components.
B. Vibronic analysis
Band 1 at 19 187 cm⫺1 is assigned as the origin of the
Ã←X 2 ⌸ transition. However, due to the large change of
geometry, the real origin might not be detected. The calcu-
lated adiabatic excitation energy is predicted ⬃0.33 eV be-
low 共Table IV兲.
The dominant vibrational progression 共bands 1, 3, 11
and 21兲 involves the CCH in-plane bending mode ␯ 4 (a ⬘ ) of
the à state. The observed negative anharmonicity is charac-
teristic of a double-well potential with levels lying below the
barrier to linearity. This high frequency of 881 cm⫺1 is com-
parable to the strongly bent 1 A ⬘ state of C3H⫺. 36 Weak tran-
sitions 共for example, bands 5 and 14兲 belong to progressions
involving the combination of the carbon skeleton stretching
modes ␯ 3 (a ⬘ ) and ␯ 2 (a ⬘ ) with ␯ 4 in the à state. Their fre-
quencies are 1091 and 1836 cm⫺1, respectively. The CH
stretching mode is observed through the band 23 and its
frequency is 2800 cm⫺1 as expected for a strongly bent
structure.36,37 The inferred frequencies are summarized in
Table V.
The intensity and the complexity of the vibronic system
observed at about 20 540 cm⫺1 suggest that the origin of the
second electronic transition is located in this energy region.
The most intense band 共8兲 is assigned to the origin
共K⫽0←1 component兲 of the B̃←X 2 ⌸ electronic transition.
The adiabatic excitation energy is calculated to be lower by
⬃0.33 eV similar to the à state 共Table IV兲. Unlike for the Ã
state, the origin is strong because the change of geometry is
smaller for the B̃ state as shown by ab initio calculations.
Interaction between these two states can be regarded as Co-
riolis coupling with the selection rules: ⌬K⫽0 for parallel
and ⫾1 for perpendicular Coriolis coupling. The levels with
K⫽0 are not affected and the perturbation is increasing with
K and v . 38 Thus only the transitions involving levels with
K⫽0 of the states are used for assignment. The A constant in
the B̃ state is ⬃40 cm⫺1 close to the ab initio value 共Table
IV兲. The K⫽2←1 component 共band 10兲 is found to be
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Electronic spectrum of C3H 6917
rather weak and this can be due to mixing with the lower
state. Above 22 000 cm⫺1, the spectrum indicates that the
mixing between the two electronic states becomes important
region 共Fig. 2兲.
Band 7 is identified as the K⫽0←1 component of the
␯ 5 (a ⬘ ) CCC bending mode of the à state (460 cm⫺1) ob-
served as a first member of a progression of combination
bands with ␯ 4 . The ␯ 5 frequency is consistent with theoret-
ical values 共Table V兲. Two peaks below and above the ex-
pected K⫽2←1 component are found 共bands 9兲. This split-
ting is due to a Fermi resonance between the levels 共000110兲
with K⫽2 and 共000030兲 with K⫽2 in the à state 共⌬K⫽0,
⫾1 selection rule for the interaction兲. Further mixing with
the 0 00 (K⫽2) level in the B̃ state cannot be excluded and
could explain the rather strong intensity of these two bands.
Band 14 is assigned to the K⫽0←1 component of the next
member of this progression. Again the second component
K⫽2←1 is not observed at the expected position.
The frequency of the CCC bending mode ␯ 5 (a ⬘ ) in the
B̃ state is 493 cm⫺1, according to the band 13 assignment.
Band 17 is the first member of another progression involving
the CCH in-plane bending mode ␯ 4 (a ⬘ ) in the B̃ state. Its
frequency (783 cm⫺1) is smaller than in the à state 共Table
V兲.
In the energy region above 23 000 cm⫺1, the spectrum
shows a very different behavior and the vibronic bands are
much broader. These bands probably arise from another elec-
tronic state. Based on the ab initio calculations these are
assigned to the C̃ 2 A ⬙ ←X 2 ⌸ electronic transition. The
bands observed in the R2C2PI spectrum and their assign-
ment are given in Table I.
C. Role of the CCH bending motion
The role of the CCH bending motion ( ␯ 4 ) is emphasized
by the calculations and the spectrum. With these results the
potential curves along the CCH angle can be approximated
共Fig. 4兲. The analytical function used for the double-well
potential curves is quadratic plus a Lorentzian hump. It has
shown to provide the best fit of the vibrational progression
involving CCH bending mode in the C3H⫺ anion.37 The im-
portance of the vibronic coupling resulting from this bending
motion can be inferred from these potential curve, as is
pointed out in theoretical studies of linear molecules.39,40
In case of the à 2 A ⬘ ( 2 ⌬) potential curve, the vibrational
progression is fitted as for C3H⫺. 37 The same reduced mass
␮ ⫽1.15 has been used and the angle 115° is deduced from
the measured A constant. Only the shape parameter and the
barrier height H A are fitted in order to reproduce the vibra-
tional progression 共root mean square 13 cm⫺1). The fitted
barrier height is 4750 cm⫺1 placing the barrier to linearity at
⬃23 500 cm⫺1. This value is close to the ab initio value of
the 2 ⌬ state 共Table III兲. The calculations yields a value for
H A of 7350 cm⫺1. The discrepancy is equal to the difference
in the adiabatic excitation energies 共see Sec. V B兲. It is due to
an overestimation of the stabilization of the bent structure in
these CASSCF calculations as was seen for the ground state.
6918 J. Chem. Phys., Vol. 115, No. 15, 15 October 2001 Ding et al.

can be disregarded for a qualitative discussion because it is

placed 1 eV above the 2 ⌸ one and coupling requires higher
order terms.39 The CCH bending motion lowers the symme-
try to C s and gives rise to strong interaction between the
components of the same symmetry. Vibronic couplings lead
to nonlinear geometries in the excited states of l-C3H.
The role of the other coordinates is not considered here
although large changes in the CC bond lengths are predicted.
However, the CCH bending motion appears to be the most
active one since it breaks the symmetry. Accurate potential
surfaces are needed to confirm the presence of a conical in-
tersection between the X 2 ⌸( 2 A ⬙ ) and the à 2 A ⬘ as sug-
gested in Fig. 4. The short lifetime 共sub-ps兲 derived from the
band profile can be interpreted as due to this conical inter-
section.

VI. CONCLUSION
The electronic spectrum of C3H was observed for the
first time under low temperature conditions as in the inter-
stellar medium. This study reveals a rich and complex vi-
bronic system in the visible. Both l-C3H and c-C3H have
been detected in the dense and translucent clouds by
radioastronomy.4,41 The data suggest column densities of
⬃1012 cm2 in the diffuse clouds, and using the calculated
oscillator strength and Franck–Condon factors would imply
that the equivalent width for the strongest vibronic band in
the visible would be ⬃0.1 mÅ, well below the actual detec-
tion limit of diffuse interstellar band absorptions.

FIG. 4. Potential curves along the CCH bending coordinate for the first
ACKNOWLEDGMENTS
electronic states of l-C3H. The solid lines belong to the A ⬘ and the dashed
to A ⬙ symmetry. The symmetries of the states at the linear geometry are The authors would like to thank Professor Pavel Rosmus
given.
for helpful discussions. This work has been supported by the
Swiss National Science Foundation 共Project No. 20-
A higher level of theory might give more accurate values. 63459.00兲.
The potential curve is plotted in Fig. 4. The simulated
1
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