Journal of Molecular Spectroscopy 263 (2010) 93–100

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Journal of Molecular Spectroscopy

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Vibronic structure of the 3s Rydberg state of the 2-methylallyl radical

Michael Gasser, Jann A. Frey, Jonas M. Hostettler, Andreas Bach *
Laboratorium für Organische Chemie, ETH Zürich, CH-8093 Zürich, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: Resonance-enhanced multiphoton ionization combined with electronic ground state depletion spectros-
Received 4 June 2010 copy of jet-cooled 2-methylallyl (C4H7) radicals provides vibronic spectra of the 3s and 3p Rydberg states.
In revised form 19 July 2010 Analysis of the vibronic structure following one-photon and two-photon excitation of rovibronically cold
Available online 23 July 2010
2-methylallyl radicals and its isotopologues C4H4D3 and C4D7 reveals transitions to more than 30 vibra-
tional levels in the 3s Rydberg state that are identified and reassigned on the basis of predictions from ab
Keywords: initio calculations and results from pulsed-field-ionization zero-kinetic-energy photoelectron spectra
2-Methylallyl
obtained with resonant multiphoton excitation via selected intermediate states. Depletion spectroscopy
Free radicals
Multiphoton ionization
reveals transitions to short-lived 3p Rydberg states that have a large oscillator strength.
Rydberg states Ó 2010 Elsevier Inc. All rights reserved.

1. Introduction Here we revisit the electronic spectrum of the 2-methylallyl

radical in the spectral region of the 3s Rydberg state. We probe
A considerable effort in the last decades has provided a detailed the vibronic structure of three different isotopologues of jet-cooled
understanding of the electronic structure, the dissociation dynam- 2-methylallyl radicals using REMPI spectroscopy combined with
ics and the reactivity of many small hydrocarbon radicals. The UV/UV depletion spectroscopy as shown schematically in Fig. 1.
2-methylallyl radical has been studied using a range of spectro- Analyzing the vibronic structure following one-photon excitation
scopic methods including electron spin resonance [1], photoelectron allows us to identify and assign transitions to the 3s and the 3p
[2], absorption [3,4], resonance Raman [5,6], and photofragment ac- Rydberg states on the basis of predictions from ab initio calcula-
tion spectroscopy [7]. The 2-methylallyl radical was first produced tions and information on the photoionization dynamics provided
in the gas phase by Callear and Lee [3] by pyrolysis of various radical by pulsed-field-ionization zero-kinetic-electron (PFI-ZEKE) photo-
precursors. The authors reported a structured absorption in the electron as well as photoionization spectroscopy.
ultraviolet (UV) in the range between 220 and 260 nm. Hudgens
and Dulcey [8] later measured resonance-enhanced multiphoton
2. Experimental
ionization (REMPI) spectra of the 2-methylallyl radical and assigned
a prominent band following two-photon excitation to the electronic
The experimental apparatus is a modified version of a molecular
origin of the 3s Rydberg state, an assignment which was later con- beam machine described previously [11]. Briefly, we generate a
firmed [9]. Chen et al. measured the 1+1 REMPI spectrum of 2-meth-
clean pulse of 2-methylallyl radicals by photolysis of either
ylallyl in the same spectral range and assigned bands to transitions 3-iodo-2-methylprop-1-ene [7], 3-bromo-2-methylprop-1-ene
to several different electronic states with p* character based on ab
(Aldrich Chemicals) or 3-methylbut-3-enyl nitrite [7] and 3-[2H]3-
initio calculations [9]. methylbut-3-enyl nitrite [7] as well as perdeuterated 3-bromo-2-
We recently investigated the vibronic structure of the allyl rad-
methylprop-1-ene (see Supplementary data) for the isotopically
ical in the energy range of its 3s Rydberg state [10,11], which is ex- labeled radicals. We expanded the radical precursor seeded in 3
pected to have a similar electronic structure as the 2-methylallyl
bar of helium into a synthetic fused silica capillary tube (internal
radical. The prominent and complex vibronic structure observed diameter: 0.8 mm, length: 22 mm) attached to the 0.8 mm orifice
following one-photon excitation was shown to arise from vibroni-
of a 20 Hz pulsed valve (General Valve Series 9) [12]. The fourth har-
cally allowed transitions to the Bðe 2 A1 Þ 3s Rydberg state and transi-
monic output (266 nm) of a Nd:YAG laser (Spectra Physics, GCR ser-
tions to the C e ð2 B2 Þ 3py Rydberg and the short-lived e Eð2 B1 Þ 3px
ies) or the 193 nm output of an excimer laser (Radiant Dyes EXC-5)
Rydberg state with no evidence for transitions to valence excited provided UV light for photolysis of the radical precursor in the fused
states.
silica capillary tube approximatively 2 mm from its exit.
The output of a Nd:YAG-pumped dye laser (Radiant Dyes
* Corresponding author. Fax: +41 44 632 1280. Narrowscan) provided UV or visible light needed for recording
E-mail address: bach@org.chem.ethz.ch (A. Bach). the 1+1 and 2+2 REMPI spectra of the 2-methylallyl radical. We

0022-2852/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.jms.2010.07.008
94 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100

(SA-MCSCF) method with a CAS(3,7) active space containing the

three p-orbitals and the 3s and 3p Rydberg orbitals. For geometry
optimizations we used the DZP basis set of Dunning [16] and we
~ augmented the carbon atom basis with two diffuse s and p func-
X+
tions using the exponents from the diffuse part of the Dunning-
3p Hay DZ++ basis set [17]. We calculated the harmonic vibrational
frequencies of the excited states at the MCSCF level of theory and
scaled them by a factor of 0.914 [18]. To obtain more accurate exci-
Energy

tation energies we also calculated the adiabatic excitation energies

of the five lowest doublet excited states of the 2-methylallyl radi-
~ 1 cal at the multi reference configuration interaction singles and
y ~ B 25
B 3s doubles (MR-CISD) level of theory using the Molpro program pack-
H H age [19] with the d-aug-cc-pVQZ basis set without the diffuse d, f
H and g functions. We also optimized the geometry of the 2-methyl-
allyl radical cation and calculated the anharmonic vibrational fre-
H H z quencies [20] using the HCTH147/TZ2P level of theory [21,22].
x
The ground electronic state and the 3s and 3p Rydberg state of
Δt the 2-methylallyl radical have a planar geometry with an almost
H H
free methyl rotor and we chose to use the Cs point group in our cal-
~
X culations with the four carbon atoms in the mirror plane, see Fig. 1.
(a) (b) (c) The adiabatic excitation energies obtained at the MR–CISD level of
theory including the zero-point energy correction derived from the
Fig. 1. Schematic energy level diagram for multiphoton ionization of the 2-
scaled MCSCF harmonic vibrational frequencies along with the cal-
methylallyl radical, C4H7. (a) 2+2 resonance-enhanced multiphoton ionization; (b)
1+1 resonance-enhanced multiphoton excitation (c) the depletion method where
culated oscillator strengths are listed in Table 1, which also in-
the absorption of the short-lived 3p Rydberg state(s) is measured by depletion of cludes the more appropriate C2v symmetry designations of the
the ground state population probed by a second laser pulse delayed by Dt = 100 ns, electronic states of 2-methylallyl. The 3s Rydberg state is predicted
which monitors the ion signal intensity using 1+1 REMPI via the B25 e 1 state. A
to lie at 4.85 eV, which is slightly lower in energy than in the allyl
schematic representation of the 2-methylallyl radical and the definition of the
radical [11]. Our ab initio calculations predict that only the transi-
principal axis system are also shown.
tions to the nearly degenerate 3px and the 3py Rydberg states carry
used a collimated laser beam with a pulse energy of 1–2 mJ/pulse for significant oscillator strength.
recording the 1+1 REMPI spectra and used a 300 mm focal length
lens to focus the fundamental dye laser output (4.5 mJ/pulse) into
the skimmed radical beam in the source of a linear time-of-flight 4. Experimental results and analysis
mass-spectrometer (TOF-MS) to obtain the 2+2 REMPI spectra. The
ions were detected using double microchannel plates. Fig. 2 shows the 2+2 and 1+1 REMPI spectra and the UV/UV
We used the output of a second dye laser (Radiant Dyes Nar- depletion overview spectrum in the range from 38 200 cm1 to
rowscan) pumped by another Nd:YAG laser (Spectra Physics, GCR 43 300 cm1 of the 2-methylallyl radical appears in Fig. 3. For the
series), which was aligned antiparallel with the REMPI detection present work, we use predictions from high-level ab initio calcula-
laser beam to record UV/UV depletion spectra. We tuned the RE- tions along with isotopic band shifts to assign the multitude of
MPI detection laser to an intense transition while scanning the bands in the spectra of 2-methylallyl radicals.
depletion laser as shown schematically in Fig. 1 to obtain the UV/
UV depletion spectra. A laser shot-by-shot subtraction scheme of 4.1. The 2+2 REMPI spectrum
the ion signal intensity yielded the depletion spectrum. We rou-
tinely observed a REMPI signal intensity depletion of 50–60% at A prominent band appears in the 2+2 REMPI spectrum of 2-
a time delay Dt = 100 ns between the laser pulses optimized for methylallyl shown in Fig. 2a centered at 38 342 cm1, which corre-
maximum ion signal depletion. We calibrated all spectra by mon- e
sponds to the electronic origin of the B-state, the 3s Rydberg state
itoring the laser wavelength during each scan with a pulsed wave- forbidden in one-photon excitation [8,9]. In addition to a band at
length meter (Toptica Photonics, WS6). +458 cm1 assigned to the C–C–C bending mode (m17), we also ob-
In the PFI-ZEKE photoelectron experiments, a single pulse of serve an intense band at +379 cm1 corresponding to the funda-
12 V/cm applied after a field-free delay time of 0.9 ls was used mental of the CH3 in-plane bending mode (m18), in agreement
to extract the PFI-ZEKE photoelectrons into a 75 mm-long field-free with the previous study of Chen et al. [9]. The wave number calcu-
drift tube at the end of which they were detected on double micro- lated ab initio for those modes agrees to within 5% of the experi-
channel plates. We applied a correction of 5.8 cm1 to obtain the mental value, see Table 2. The large change in the C–C–C bond
field-free ionization thresholds for the PFI-ZEKE experiments using
the procedure described in Ref. [13].pWe ffiffiffi used a correction of
DE = 82.6 cm1 calculated with DE ¼ c F for the photoionization
efficiency (PIE) curves to compensate [14] for the shift of the ioniza- Table 1
Adiabatic and zero-point energy corrected excitation energies and oscillator strengths
tion thresholds induced by the static electric field F = 183.4 V/cm in
(a.u.) of the 2-methylallyl radical obtained at the MR–CISD level of theory.
our TOF-MS. We used a factor c = 6.1 determined [15] using a least
squares fit of the apparent ionization energies measured at four dif- Electronic Excitation State Oscillator Experimental exc.
e 1 state.
ferent static electric fields following excitation to the B25 state Cs/C2v energy (eV) character strength energy (eV)
22A00 /12B1 2.86 p* 7.0  106
3. Computational methods and results 12A0 /12A1 4.85 3s 1.3  103 4.75
22A0 /22A1 5.50 3py 4.1  105
32A00 /22B1 5.55 3px 0.039 5.2
We optimized the geometries of the 2-methylallyl radical using 32A0 /12B2 5.59 3pz 0.015 5.2
the state averaged multiconfiguration self-consistent field
 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100 95

(a) C4H 7 251

241 1 1
25 18 1+1 REMPI
1
26

~ 0
B0
1
18 17
1
2+2 REMPI
Ion signal / arb. units

(b) C4H4D3
1+1 REMPI

2+2 REMPI

(c) C4 D 7
1+1 REMPI

2+2 REMPI

0 200 400 600 800 1000 1200 1400

-1
wave number relative to vibrationless state / cm

Fig. 2. The REMPI spectra of the (a) C4H7, (b) C4H4D3 and (c) C4D7 isotopologues of the 2-methylallyl radical. The vertical scale has been chosen so that the maxima of the
spectra have similar amplitudes and do not reflect the relative photoionization signals. The 1+1 REMPI spectra of C4H7 and C4D7 correspond to a magnification of the spectra
shown in Fig. 3.

angle following electronic excitation gives rise to a short progres- 4.2. The PFI-ZEKE photoelectron spectra and PIE curves
sion in the C–C–C bending mode with the first overtone visible at
+863 cm1 and a corresponding diagonal anharmonic constant In the same spectral range as following two-photon excitation
[23] of x1717 = 26.5 cm1, which is somewhat larger than the e
to the B-state, a large number of bands with a complex vibronic
analogous anharmonic constant in the allyl radical [11]. We also structure also appear in the 1+1 REMPI spectra, see Figs. 2 and 3.
e 2 state. Towards higher wave
assign a band at +735 cm1 to the B18 To help unravel the complex vibronic structure in the 38 200
number, several weaker and somewhat diffuse bands appear that cm1 to 41 500 cm1 range for 2-methylallyl visible in the 1+1 RE-
e 1 and the B15
we tentatively assign to the B16 e 1 state with funda- MPI spectra, we recorded PFI-ZEKE photoelectron spectra as well as
mental wave numbers of m ~16 ¼ 846 cm 1
and m~15 ¼ 940 cm1 , PIE curves via selected intermediate states of 2-methylallyl.
again with a deviation from the calculated values of <5%. Fig. 4b shows the 1+10 PFI-ZEKE photoelectron spectra re-
In the 2+2 REMPI spectra of C4H4D3 and C4D7 a similar pattern is corded via the first three prominent transitions visible in the
observed as in the non-deuterated species, see Fig. 2b and c. The 1+1 REMPI spectrum. The photoionization efficiency curves of
electronic origin of the B e e transition of 2-methylallyl shifts
X 2-methylallyl [Fig. 4a] exhibit a sharp rise from zero at the posi-
by 16 cm1 to higher wave number for the partially deuterated tion of the lowest band of the PFI-ZEKE photoelectron spectra,
and by 56 cm1 for the fully deuterated 2-methylallyl radical, which confirms that the photoelectron signal indeed arises from
respectively. Comparing the band intensities in the 2+2 REMPI 2-methylallyl radicals. In all PFI-ZEKE photoelectron spectra only
spectrum of C4H7 and C4D7 reveals that the bands towards higher a single band is visible, which indicates that the intermediate
wave number are more prominent for the deuterated radical, state used in the 1+10 excitation scheme has a similar potential
which we tentatively explain with longer excited-state lifetimes energy surface as the cationic ground state. The band positions
for the deuterated radical, see also below. In addition to the funda- observed in the PFI-ZEKE photoelectron spectra are listed in Table
mentals and overtones observed in the 2+2 REMPI spectrum of 2- 5. We also attempted to record PFI-ZEKE photoelectron spectra in
methylallyl, several additional bands can be assigned in the 2+2 e 0 state of 2-methylallyl, but no 2+10 RE-
2+10 excitation via the B0
REMPI spectrum of the two isotopologues. Two fundamentals MPI ion signal could be observed, presumably because of a loss of
(m14 and m13) are assigned, based on the good agreement of the cal- ion signal arising from the trigger jitter of the two individually
culated wave numbers to the experimental values and of the isoto- pumped multi-mode dye lasers pulses for a short-lived intermedi-
pic band shifts, see Table 3. The band positions and assignments of ate state.
all vibrational levels observed in the REMPI spectra for the 3s The excited-state lifetime of fully deuterated 2-methylallyl
Rydberg state appear in Table 4. appears to be slightly longer, as a 2+10 REMPI ion signal via the
96 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100

(a) C4H 7

~ 1
B 25 1 1
25 18 1
19 1+1 REMPI

Ion signal / arb. units

Depletion

(b) C4D 7

~ 1
B 25 1+1 REMPI

Depletion

39000 40000 41000 42000 43000

wave number / cm-1

Fig. 3. The 1+1 REMPI spectra (top traces) and the UV/UV depletion spectra (bottom) traces of the (a) C4H7 and (b) C4D7 isotopologues of the 2-methylallyl radical in the range
38 200–43 300 cm1. The depletion spectra were obtained by monitoring the UV-laser depletion of the ion signal intensity produced with 1+1 REMPI via the B e 251 state. The
vertical scale has been chosen so that the maxima of the spectra have similar amplitudes and do not reflect the relative photoionization signals.

Table 2 intermediate states that give rise to the first few bands visible in
Calculated vibrational frequencies in cm1 of the 2-methylallyl radical for the 3s both the 1+1 REMPI and 2+2 REMPI spectra. The photoionization
Rydberg state (MCSCF/DZP++, scaled by 0.914) and anharmonic vibrational frequen- efficiency curves for C4D7 obtained via five different intermediate
cies for the C4D7 cation obtained at the HCTH147/TZ2P level of theory.
states are displayed in Fig. 5. The adiabatic ionization energy of
Mode 3s X+ d7-2-methylallyl determined from the PIE curve obtained via the
e 0 state is 63 530(10) cm1 (7.877(1) eV).
B0
C4H7 C4H4D3 C4D7 C4D7
The ionization energies extracted from the five photoionization
a0
m1 3157 3157 2357 2333 efficiency curves are different, which is inconsistent with the pre-
m2 3151 3151 2354 2337 vious assignments of the first two bands visible in the 1+1 REMPI
m3 3040 3040 2247 2217 spectrum of 2-methylallyl radical to electronic origins of two ex-
m4 3036 3036 2222 2196
cited states with p* character [9]. The very sharp rise of the PIE
m5 3027 2247 2216 2239
m6 2937 2113 2113 2106
curves and the fact that only a single band is visible in the PFI-ZEKE
m7 1572 1567 1477 1441 photoelectron spectra together with the different ionization ener-
m8 1544 1543 1430 1384 gies strongly suggests that the bands visible in the 1+1 REMPI spec-
m9 1469 1050 1049 1017 trum correspond to vibronically allowed transitions to the 3s
m10 1433 1413 1152 1112
Rydberg state in 2-methylallyl. This is similar to the allyl radical,
m11 1387 1102 1064 1038
m12 1377 1375 1058 1040 where the 3s Rydberg state also has a geometry that is very similar
m13 1057 1004 844 833 to that of the cationic ground state leading to Dm = 0 transitions
m14 1033 1030 839 831 that are particularly intense in the PFI-ZEKE photoelectron spectra
m15 969 812 740 720
[10]. The wave numbers of several vibrational levels of the C4D7
m16 824 770 723 722
m17 434 427 363 370
cation inferred from the PIE curves are listed in Table 5 and they
m18 378 344 318 325 generally agree to within the estimated experimental uncertainty
a00
to the predictions made at the HCTH147/TZ2P level of theory, see
m19 3018 2237 2237 2242 also Table 2.
m20 1463 1051 1053 1021
m21 1092 1091 867 878
4.3. The 1+1 REMPI spectrum
m22 1079 1076 905 916
m23 1043 859 816 795
m24 650 650 461 432 Fig. 2 shows the 1+1 REMPI spectra of three isotopologues of the
m25 494 452 405 375 2-methylallyl radical. Compared to the first 1+1 REMPI spectrum
m26 308 306 232 144
[9] that was measured using a pyrolysis radical source, we achieve
m27 23 16 16 29
a lower rovibrational temperature and therefore an improved spec-
tral resolution that allows for a more detailed analysis of the vib-
e 0 state could be observed, allowing us to measure photoioniza-
B0 ronic structure and a more accurate determination of the band
tion efficiency curves in both 2+10 and 1+10 excitation via the positions.
 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100 97

Table 3
Summary of all the observed experimental fundamental vibrational frequencies for the three different isotopologues of 2-methylallyl in the 3s
Rydberg states. The relative deuterium shifts with respect to C4H7 are given together with the calculated values (in brackets).

Isotopologue C4H7 C4H4D3 C4D7

Mode Description m~=cm1 m~=cm1 Ratio (%) m~=cm1 Ratio (%)

a0
m13 as CH ip bend 1035 975 94 (95) 844 82 (80)
m14 s CH2 bend 1020 1019 100 (100) 844 83 (81)
m15 as CH ip bend 940 788 84 (84) 741 77 (76)
m16 s CC stretch 846 788 93 (93) 741 88 (88)
m17 CCC bend 458 453 99 (98) 371 81 (84)
m18 CH3 ip bend 379 376 99 (91) 293 77 (84)
a00
m19 as CH3 C–H stretch 2915 2195 75 (74) 2192 75 (74)
m20 as CH3 C–H bend 1485 1066 72 (72) 1061 71 (72)
m21 as CH2 oop bend 1188 1198 101 (100) 956 80 (79)
m22 s CH2 oop bend 1113 903 81 (84)
m23 s CH2 oop bend 1034 844 82 (82) 798 77 (78)
m24 as CH2 twist 623 626 100 (100) 444 71 (71)
m25 CH3 oop bend 448 411 92 (91) 367 82 (82)
m26 s CH2 twist 184 185 100 (99) 137 74 (75)

Table 4
Band maxima in cm1 and assignments of the bands observed in the 1+1 and 2+2 REMPI spectra of the 2-methylallyl radical isotopologues (C4H7, C4H4D3, C4D7).

Experiment Assignment C4H7 C3H4D3 C4D7

Band max rel. Band max rel. Band max rel.
2+2 00 38 342 0 38 358 0 38 398 0
1+1 261 38 526 +184 38 543 +185 38 535 +137
2+2 181 38 721 +379 38 734 +376 38 691 +293
1+1 251 38 790 +448 38 769 +411 38 765 +367
2+2 171 38 800 +458 38 811 +453 38 769 +371
1+1 261181 38 891 +549 38 903 +545 38 827 +429
1+1 241 38 965 +623 38 984a +626a 38 842 +444
1+1 261171 39 013 +671 38 984a +626a 38 919 +521
2+2 182 39 077 +735 39 083 +725 38 976 +578
1+1 251181 39 177 +835 39 151 +793 39 067 +667
2+2 161 39 188a +846a 39 146a +788a 39 139a +741a
2+2 181171 39 188a +846a 39 211a +853a 39 082 +684
2+2 172 39 205 +863 39 211a +853a 39 139a +741a
1+1 251171 39 254 +912 39 223 +865 39 137a +739a
2+2 151 39 282 +940 39 146a +788a 39 139a +741a
1+1 241181 39 342 +1000 39 356 +998 39 137a +739a
1+1 261181171 39 354 +1012 39 333 +975 39 237 +839
1+1 231 39 376 +1034 39 202 +844 39 196 +798
2+2 141 39 362 +1020 39 377 +1019 39 242a +844a
2+2 131 39 377 +1035 39 333 +975 39 242a +844a
1+1 241171 39 419 +1077 39 433 +1075 39 211 +813
1+1 221 39 455 +1113 – – 39 301a +903a
1+1 211 39 530 +1188 39 556a +1198a 39 354 +956
1+1 251182 39 567 +1225 39 502 +1144 39 369 +971
1+1 251181171 39 635 +1293 39 623 +1265 39 459a +1061a
1+1 251161 39 657 +1315 39 556a +1198a 39 512 +1114
1+1 251172 39 691 +1349 39 708 +1350 39 523 +1125
1+1 241161 39 810 +1468 39 791 +1433 39 611 +1213
1+1 201 39 827 +1485 39 424 +1066 39 459a +1061a
1+1 211171 40 000 +1658 40 007 +1649 39 748 +1350
1+1 251181161 40 022 +1680 39 936 +1578 39 830 +1432
1+1 201181 40 216 +1874 39 829 +1471 39 762 +1364
1+1 201171 40 310 +1968 39 868 +1510 39 844 +1446
1+1 191 41 257 +2915 40 553 +2195 40 590 +2192
1+1 191181 41 636 +3294 40 930 +2572 40 887 +2489
1+1 191171 41 711 +3369 41 005 +2647 40 961 +2563
a
Approximate value due to overlapping bands.

The first prominent band in the 1+1 REMPI spectrum of 2-meth- predict a relative deuterium shift for the CH3 oop bending mode
e
ylallyl appears at +448 cm1 relative to the B-state origin, which (m25) of 91% for the partially deuterated and 82% for fully deuter-
e 1 state. This band shifts to +411 cm1
we here reassign to the B25 ated 2-methylallyl, in excellent agreement with the experimental
for C4H4D3 and to +367 cm1 for d7-2-methylallyl, which corre- observation; see Table 3. The scaled harmonic vibrational fre-
sponds to 92% and 82%, respectively, of the wave number for the quency for that mode calculated ab initio, however, is 10% too high.
251 vibrational level in 2-methylallyl. Our ab initio calculations The same observation also holds true for the lowest frequency
98 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100

(a) 1+1′ photo ionization efficiency curves

Ion signal / arb. units

~ 1
B 25
0

~ 1
B 24
0

~ 1 1
0 B 25 18

(b) 1+1′ PFI-ZEKE

251
Photoelectron signal / arb. units

~ 1
B 25

241

~ 1
B 24

251181
~ 1 1
B 25 18

63900 64100 64300 64500

wave number / cm-1

Fig. 4. (a) The 1+10 PIE and (b) the 1+10 PFI-ZEKE photoelectron spectra of C4H7 in the range 63 800–64 700 cm1. The vertical scale has been chosen such that the maxima of
the spectra have the same amplitude.

Table 5 of all observed fundamental vibrational levels is listed in Table 3

Experimental cation vibrational frequencies of C4D7 extracted from the PIE curves and for all isotopologues of 2-methylallyl.
band positions in cm1 of the vibrational levels of the C4H7 cation observed in the PFI-
ZEKE photoelectron spectra. The uncertainty in the experimental wave numbers is
In addition to these fundamentals in the 1+1 REMPI spectrum,
estimated to be ±10 cm1. we also observe a large number of combination bands involving
the totally symmetric vibrational levels that appear prominently
C4H7 C4D7
in the 2+2 REMPI spectrum including the C–C–C bending mode
Vibrational level Band center m þexpt =cm1
e
(m17) and the CH3 in-plane bend (m18). The first such prominent
181 310 combination band appears at +835 cm1 in the 1+1 REMPI spec-
251 64 066 382
trum that we assign to the 251181 state, see Fig. 2a. The corre-
241 64 244 450
251181 64 458 688 sponding combination with the C–C–C bending mode, the 251171
state, also appears prominently at +912 cm1. Analogous to the
vibronically allowed vibrational levels of the 3s Rydberg state ob-
served and assigned for the allyl radical in the 1+1 REMPI spec-
e
vibration in the B-state, where the calculated wave number for the trum, combination bands involving the C–C–C bending mode also
CH2 twisting mode is e m 26 ¼ 308 cm1 for C4H7 (see Table 2) and the appear particularly intense in 1+1 REMPI spectrum in 2-methylal-
corresponding band in the 1+1 REMPI spectrum appears at lyl, which can be rationalized with the large change in the C–C–C
+184 cm1. The same discrepancy between calculated and ob- bond angle following electronic excitation. A list of all band posi-
served values for the lowest frequency vibration was also observed tions observed in the 1+1 REMPI spectra and their assignments ap-
e
in the allyl radical in the B-state, presumably because of the rather pears in Table 4.
anharmonic potential for the low-frequency CH2 twisting mode
[11]. The observed and calculated relative deuteration shifts for
m26, however, are in excellent agreement. We also observe a band 4.4. The UV/UV depletion spectra
at +623 cm1 in the 1+1 REMPI spectrum of C4H7 that we assign
e 1 state. The calculated wave number for this asymmetric
to the B24 Our high-level ab initio calculations predict that the transitions
(as) CH2 twisting mode agrees to within 4% to the observed wave to the 3px Rydberg state in the 2-methylallyl radical has an oscilla-
number for the 241 level and again the relative deuteration shifts tor strength of 0.039 and that for the 3pz Rydberg state fosc = 0.015,
are in good agreement. We also observe bands assigned to many see Table 1. The calculated adiabatic excitation energies of these
other fundamentals in the 1+1 REMPI spectrum and a summary two 3p Rydberg states differ only by 0.04 eV. In the 1+1 REMPI
 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100 99

(a) 2+1′ photo ionization efficiency curves

~ 0
B0
0

~ 1
B 18
0
Ion signal / arb. units

(b) 1+1′ photo ionization efficiency curves

~ 1
B 25
0

~
B 241
0

~ 1 1
B 25 18
0

63500 63700 63900 64100 64300

-1
wave number / cm

Fig. 5. (a) The 2+10 and (b) the 1+10 PIE curves of the d7-2-methylallyl radical (C4D7) obtained via different intermediate states. The vertical scale has been chosen so that the
maxima of the spectra have similar amplitudes and do not reflect the relative photoionization signals.

overview spectrum shown in Fig. 3a of 2-methylallyl, the vibronic transitions to the 3pz and the 3px Rydberg states carry a large oscil-
band intensities rapidly decrease to higher wave number, while in lator strength and we therefore assign the broad bands to transi-
the corresponding spectrum for d7-2-methylallyl shown in Fig. 3b tions either to the 3pz and/or to the 3px Rydberg states. Given the
the intensities decrease less quickly, presumably because of longer very small energy difference between the calculated adiabatic exci-
excited-state lifetimes for the vibrational levels of the 3s Rydberg tation energies of the 3pz and the 3px Rydberg states of only 0.04 eV
state in fully deuterated 2-methylallyl as already mentioned in (323 cm1), we cannot unambiguously assign the broad features
Section 4.1. We have recorded UV/UV depletion spectra in order visible in the UV/UV depletion spectra to either of those 3p Ryd-
to reveal transitions to the possibly short-lived 3p Rydberg states berg states. At least up to 43 400 cm1, we did not observe any
of 2-methylallyl. additional bands in the UV/UV depletion spectra.
In the UV/UV depletion spectra in shown Fig. 3 a few weak and Upon deuteration of 2-methylallyl, the broad spectral feature
very sharp bands appear at identical band positions as in the 1+1 shifts to slightly higher wave number, similar to the electronic ori-
REMPI spectrum that we have assigned to vibronically allowed gin of the 3s Rydberg state that shifts only by +56 cm1 upon deu-
transitions to the 3s Rydberg state. To higher wave number in teration. In both the UV/UV depletion and the 1+1 REMPI spectrum
the UV/UV depletion spectra, a broad and continuous absorption of C4H7 a prominent band appears at 41 257 cm1 that we here
only partially visible in the 1+1 REMPI spectra appears ranging e 1 state based on the large isotopic band shifts.
reassign to the B19
from 41 750 cm1 to 42 450 cm1 for the non-deuterated and from
41 950 cm1 to 42 600 cm1 for the fully deuterated 2-methylallyl 5. Discussion and conclusions
radical, respectively. These broad spectral features most likely arise
from very short excited-state lifetimes and the band position for Resonance-enhanced multiphoton ionization combined with
C4H7 in the UV/UV depletion agrees well with the ‘‘very strong” UV/UV depletion spectroscopy of three isotopologues of jet-cooled
absorption line at 42 039 cm1 reported already by Callear and 2-methylallyl radicals provides information on the vibronic struc-
Lee [3]. The shape of our UV/UV depletion spectrum is also very ture of the 3s and the 3p Rydberg states. The electronic origin of
similar to the low resolution room temperature absorption spec- the Be 3s Rydberg state is located at 38 342 cm1 following two-
trum of 2-methylallyl reported by Nakashima et al. [4], which photon excitation, in agreement with previous studies [8,9]. The
has an absorption maximum at 42 105 cm1 for a band starting 2+2 REMPI spectra of rovibronically cold C4H4D3 and C4D7 together
at 41 500 cm1. These authors also derived an integrated oscilla- with isotopic band shifts predicted at the MCSCF level of theory al-
tor strength from 39 000 cm1 to 46 000 cm1 of fosc = 0.14. The lows to identify and assign several fundamental vibrational levels
sharp bands appearing in the UV/UV depletion spectrum to lower e
of the B-state, including the CH2 bending mode (m14).
wave number correspond to vibronically allowed transitions to Photoionization and PFI-ZEKE photoelectron spectroscopy via se-
the 3s Rydberg state and the broad bands with a width of 0 0
lected intermediate states in 1+1 and 2+1 excitation yields an adia-
700 cm1 appearing at the same position as in the absorption 1
batic ionization energy of 63 530(10) cm for d7-2-methylallyl and
spectra [3,4] must arise from a different electronic transition as provides the wave numbers of several vibrational levels in the 2-
most of the integrated oscillator strength is contained in those methylallyl cation for the first time. We reassign the vibronic bands
bands [4]. According to our ab initio calculations, only the appearing in the 1+1 REMPI spectrum in the 38 500–41 700 cm1
100 M. Gasser et al. / Journal of Molecular Spectroscopy 263 (2010) 93–100

wave number range to vibronically allowed transitions to vibra- article can be found, in the online version, at doi:10.1016/
e
tional levels of the B-state. The analysis of the vibronic structure in j.jms.2010.07.008.
the 1+1 REMPI spectrum of 2-methylallyl and its isotopologues pro-
vides the wave numbers of many vibrational levels in the 3s Rydberg
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