Chih-Hsuan Chang

Sub-Doppler Spectroscopy of the trans-HOCO Radical in the OH Stretching Mode

Rovibrational spectroscopy of the fundamental OH stretching mode of the trans-HOCO radical has been studied via sub-Doppler high-resolution infrared laser absorption in a discharge slit-jet expansion. The trans-HOCO radical is formed by discharge dissociation of H2O to form OH, which then combines with CO and cools in the Ne expansion to a rotational temperature of 13.0(6) K. Rigorous assignment of both a-type and b-type spectral transitions is made possible by two-line combination differences from microwave studies, with full rovibrational analysis of the spectrum based on a Watson asymmetric top Hamiltonian. Additionally, fine structure splittings of each line due to electron spin are completely resolved, thus permitting all three ε(aa), ε(bb), ε(cc) spin-rotation constants to be experimentally determined in the vibrationally excited state. Furthermore, as both a- and b-type transitions for trans-HOCO are observed for the first time, the ratio of transition dipole moment projections along the a and b principal axes is determined to be μ(a)/μ(b) = 1.78(5), which is in close agreement with density functional quantum theoretical predictions (B3LYP/6-311++g(3df,3pd), μ(a)/μ(b) = 1.85). Finally, we note the energetic possibility in the excited OH stretch state for predissociation dynamics (i.e., trans-HOCO → H + CO2), with the present sub-Doppler line widths providing a rigorous upper limit of >2.7 ns for the predissociation lifetime.

High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch.

Phenyl radical has been studied via sub-Doppler infrared spectroscopy in a slit supersonic discharge expansion source, with assignments for the highest frequency b2 out-of-phase C-H symmetric stretch vibration (ν19) unambiguously confirmed by ≤6 MHz (0.0002 cm(-1)) agreement with microwave ground state combination differences of McMahon et al. [Astrophys. J. 2003, 590, L61-64]. Least squares analysis of over 100 resolved rovibrational peaks in the sub-Doppler spectrum to a Watson Hamiltonian yields precision excited-state rotational constants and a vibrational band origin (ν0 = 3071.8915(4) cm(-1)) consistent with a surprisingly small red-shift (0.9 cm(-1)) with respect to Ar matrix isolation studies of Ellison and co-workers [J. Am. Chem. Soc. 2001, 123, 1977]. Nuclear spin weights and inertial defects confirm the vibrationally averaged planarity and (2)A1 rovibronic symmetry of phenyl radical, with analysis of the rotational constants consistent with a modest C2v distortion of the carbon backbone frame due to partial sp rehybridization of the σ C radical-center. Most importantly, despite the number of atoms (N = 11) and vibrational modes (3N - 6 = 27), phenyl radical exhibits a remarkably clean jet cooled high-resolution IR spectrum that shows no evidence of intramolecular vibrational relaxation (IVR) phenomena such as local or nonlocal perturbations due to strongly coupled nearby dark states. This provides strong support for the feasibility of high-resolution infrared spectroscopy in other aromatic hydrocarbon radical systems.

Spectroscopy and Dynamics of Jet-Cooled Polyynes in a Slit Supersonic Discharge: Sub-Doppler Infrared Studies of Diacetylene HCCCCH.

Fundamental, bending (ν6, ν7, ν8, ν9), and CC-stretch (ν2, ν3) hot band spectra in the antisymmetric CH stretch (ν4) region near 3330 cm(-1) have been observed and analyzed for jet cooled diacetylene (HC≡C-C≡CH) under sub-Doppler conditions. Diacetylene is generated in situ in the throat of a pulsed supersonic slit expansion by discharge dissociation of acetylene to form ethynyl (C≡CH) + H, followed by radical attack (HC≡CH + C≡C-H) to form HC≡C-C≡CH + H. The combination of (i) sub-Doppler line widths and (ii) absence of spectral congestion permits rotational structure and Coriolis interactions in the ν4 CH stretch fundamental to be observed and analyzed with improved precision. Of particular dynamical interest, the spectra reveal diacteylene formation in highly excited internal vibrational states. Specifically, multiple Π ← Π and Δ ← Δ hot bands built on the ν4 CH stretch fundamental are observed, due to doubly degenerate bending vibrations [cis C≡C-H bend (ν6), trans C-C≡C bend (ν7), trans C≡C-H bend (ν8) and cis C-C≡C bend (ν9)], as well as a heretofore unobserved Σ ← Σ band assigned to excitation of ν2 or 2ν3 CC stretch. Boltzmann analysis yields populations consistent with universally cold rotations (Trot ≈ 15 ± 5 K) and yet superthermal vibrations (Tvib ≈ 85-430 K), the latter of which is quite anomalous for the high collision densities in a slit jet expansion. In order to elucidate the physical mechanism for this excess vibrational excitation, high level ab initio CCSD(T) calculations have been pursued with explicitly correlated basis sets (VnZ-f12; n = 2,3) and extrapolated to the complete basis set (CBS) limit using MOLPRO quantum chemistry software. The results suggest that the extensive hot band structure observed arises from (i) highly exothermic CCH + HCCH addition to yield a strongly bent HCCHCCH radical intermediate (ΔH = -62.6 kcal/mol), followed by (ii) rapid fragmentation over a submerged transition state barrier (ΔH = -18.9 kcal/mol) to form vibrationally hot diacetylene + H products (ΔH = -25.6 kcal/mol), and consistent with crossed molecular beam studies by Kaiser et al. [Phys. Chem. Chem. Phys. 2002, 4, 2950.] Finally, RRKM fragmentation rates for this complex are calculated, which exceed collision frequencies in the slit jet expansion and suggest near unity quantum efficiency for diacetylene formation.

Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+

Sub-Doppler infrared rovibrational transitions in the symmetric (v1) and antisymmetric (v6) NH stretch modes of the isotopomerically substituted ND2H2+ ammonium cation are reported for the first time in a slit jet discharge supersonic expansion spectrometer. The partially H/D substituted cation is generated by selective isotopic exchange of ND3 with H2O to form NHD2, followed by protonation with H3+ formed in the NHD2/H2/Ne slit-jet discharge expansion environment. Rotational assignment for ND2H2+ is confirmed rigorously by four line ground state combination differences, which agree to be within the sub-Doppler precision in the slit jet (∼9 MHz). Observation of both b-type (ν1) and c-type (ν6) bands enables high precision determination of the ground and vibrationally excited state rotational constants. From an asymmetric top Watson Hamiltonian analysis, the ground state constants are found to be A″ = 4.856 75(4) cm-1, B″ = 3.968 29(4) cm-1, and C″ = 3.446 67(6) cm-1, with band origins at 3297.5440(1) and 3337.9050(1) cm-1 for the v1 and v6 modes, respectively. This work permits prediction of precision microwave/mm-wave transitions, which should be invaluable in facilitating ongoing spectroscopic searches for partially deuterated ammonium cations in interstellar clouds and star-forming regions of the interstellar medium.

High resolution spectroscopy of jet cooled phenyl radical: The ν1 and ν2 a1 symmetry C-H stretching modes.

A series of CH stretch modes in phenyl radical (C6H5) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a1 symmetry, ν1 and ν2, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν1 and ν2 band origins are determined to be 3073.968 50(8) cm(-1) and 3062.264 80(7) cm(-1), respectively, which both agree within 5 cm(-1) with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm(-1) blue shift between gas phase and Ar matrix values for ν1 and ν2. This differs substantially from the much smaller red shift (Δν ≈ - 1 cm(-1)) reported for the ν19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (Trot ≈ 11 K) conditions.

Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: The NH stretching mode in ND 3 H +

High-resolution rotationally resolved spectra of the N-H stretch vibrational mode (ν 1) of jet-cooled ND3H+ ions are collected and analyzed in a sub-Doppler slit-jet infrared spectrometer. The isotopomeric ammonium ions are generated by proton transfer from H3 + to ND3 in a discharge of an ND3/H2 gas mixture, whereby the slit jet expansion cools the nascent ND3H+ ions into lower rotational states. Rotational assignments are confirmed by four-line combination differences that agree to within the spectrometer precision (9 MHz). Based on precision two-line ground-state combination differences and a symmetric top Hamiltonian, the B, D J , and D JK rotational constants for the ground vibrational state of ND3H+ are determined with high precision for the first time. Approximate rotational constants for the ν 1 excited state are also determined, with a band origin at 3316.8425(19) cm-1 and in remarkable (∼0.1 cm-1) agreement with high level anharmonic theoretical predictions by Guo and co-workers [J. Phys. Chem. A, 120, 2185 (2016)]. Our results allow us to predict several low-J pure rotational transitions of ND3H+, which we hope will support future studies of this important ion in laboratory and astronomical rotational spectroscopy.

Sub-Doppler infrared spectroscopy of CH2OH radical in a slit supersonic jet: Vibration-rotation-tunneling dynamics in the symmetric CH stretch manifold

The sub-Doppler CH-symmetric stretch (ν3) infrared absorption spectrum of a hydroxymethyl (CH2OH) radical is observed and analyzed with the radical formed in a slit-jet supersonic discharge expansion (Trot = 18 K) via Cl atom mediated H atom abstraction from methanol. The high sensitivity of the spectrometer and reduced spectral congestion associated with the cooled expansion enable first infrared spectroscopic observation of hydroxymethyl transitions from both ± symmetry tunneling states resulting from large amplitude COH torsional motion. Nuclear spin statistics due to exchange of the two methyl H-atoms aid in unambiguous rovibrational assignment of two A-type Ka = 0 ← 0 and Ka = 1 ← 1 bands out of each ± tunneling state, with additional spectral information obtained from spin-rotation splittings in P, Q, and R branch Ka = 1 ← 1 transitions that become resolved at low N. A high level ab initio potential surface (CCSD(T)-f12b/cc-pvnzf12 (n = 2,3)/CBS) is calculated in the large amplitude COH torsional and CH2 wag coordinates, which in the adiabatic approximation and with zero point correction predicts ground state tunneling splittings in good qualitative agreement with experiment. Of particular astrochemical interest, a combined fit of the present infrared ground state combination differences with recently reported millimeter-wave frequencies permits the determination of improved accuracy rotational constants for the ground vibrational state, which will facilitate ongoing millimeter/microwave searches for a hydroxymethyl radical in the interstellar medium.

Sub-Doppler infrared spectroscopy of propargyl radical (H2CCCH) in a slit supersonic expansion

The acetylenic CH stretch mode (ν1) of propargyl (H2CCCH) radical has been studied at sub-Doppler resolution (∼60 MHz) via infrared laser absorption spectroscopy in a supersonic slit-jet discharge expansion, where low rotational temperatures (Trot = 13.5(4) K) and lack of spectral congestion permit improved determination of band origin and rotational constants for the excited state. For the lowest J states primarily populated in the slit jet cooled expansion, fine structure due to the unpaired electron spin is resolved completely, which permits accurate analysis of electron spin-rotation interactions in the vibrationally excited states (εaa = - 518.1(1.8), εbb = - 13.0(3), εcc = - 1.8(3) MHz). In addition, hyperfine broadening in substantial excess of the sub-Doppler experimental linewidths is observed due to nuclear spin-electron spin contributions at the methylenic (-CH2) and acetylenic (-CH) positions, which permits detailed modeling of the fine/hyperfine structure line contours. The results are consistent with a delocalized radical spin density extending over both methylenic and acetylenic C atoms, in excellent agreement with simple resonance structures as well as ab initio theoretical calculations.

High-resolution infrared spectroscopy slit-jet cooled hydroxymethyl radical(CH2OH): CH symmetric stretching mode

Hydroxymethyl radical (CH2OH) plays an important role in combustion and environmental chemistry as a reactive intermediate. Reisler’s group publisheda the first rotationally resolved spectroscopy of CH2OH with determined band origins for fundamental CH symmetric stretch state, CH asymmetric stretch state and OH stretch state, respectively. Here CH2OH was first studied via sub-Doppler infrared spectroscopy in a slit-jet supersonic discharge expansion source. Rotationally resolved direct absorption spectra in the CH symmetric stretching mode were recorded. As a result of the low rotational temperature and sub-Doppler linewidths, the tunneling splittings due to the large amplitude of COH torsion slightly complicate the spectra. Each of the ground vibration state and the CH symmetric stretch state includes two levels. One level, with a 3:1 nuclear spin statistic ratio for Ka=0/Ka=1, is labeled as “+”. The other tunneling level, labeled as “-”, has Ka=0/Ka=1 states with 1:3 nuclear spin statistics. Except for the Ka=0 ← 0 band published before b, more bands (Ka=1← 1 , Ka=0← 0− and Ka=1← 1−) were identified. The assigned transitions were fit to a Watson A-reduced symmetric top Hamiltonian to improve the accuracy of the band origin of CH symmetric state. The rotational parameters for both ground and CH symmetric stretch state were well determined.