High-resolution CH stretch spectroscopy of jet-cooled cyclopentyl radical: First insights into equilibrium structure, out-of-plane puckering, and IVR dynamics.

First, high-resolution sub-Doppler infrared spectroscopic results for cyclopentyl radical (C5H9) are reported on the α-CH stretch fundamental with suppression of spectral congestion achieved by adiabatic cooling to Trot ≈ 19(4) K in a slit jet expansion. Surprisingly, cyclopentyl radical exhibits a rotationally assignable infrared spectrum, despite 3N - 6 = 36 vibrational modes and an upper vibrational state density (ρ ≈ 40-90 #/cm-1) in the critical regime (ρ ≈ 100 #/cm-1) necessary for onset of intramolecular vibrational relaxation (IVR) dynamics. Such high-resolution data for cyclopentyl radical permit detailed fits to a rigid-rotor asymmetric top Hamiltonian, initial structural information for ground and vibrationally excited states, and opportunities for detailed comparison with theoretical predictions. Specifically, high level ab initio calculations at the coupled-cluster singles, doubles, and perturbative triples (CCSD(T))/ANO0, 1 level are used to calculate an out-of-plane bending potential, which reveals a C2 symmetry double minimum 1D energy surface over a C2v transition state. The inversion barrier [Vbarrier ≈ 3.7(1) kcal/mol] is much larger than the effective moment of inertia for out-of-plane bending, resulting in localization of the cyclopentyl wavefunction near its C2 symmetry equilibrium geometry and tunneling splittings for the ground state too small (<1 MHz) to be resolved under sub-Doppler slit jet conditions. The persistence of fully resolved high-resolution infrared spectroscopy for such large cyclic polyatomic radicals at high vibrational state densities suggests a "deceleration" of IVR for a cycloalkane ring topology, much as low frequency torsion/methyl rotation degrees of freedom have demonstrated a corresponding "acceleration" of IVR processes in linear hydrocarbons.

Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis-HCOOH conformer.

High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H2 mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch (ν1) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. The observed signal dependence on H2 in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic "up-hill" internal rotor isomerization between trans- and cis-formic acid conformers.

High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region.

First high-resolution spectra of cold (∼35 K) singlet bromomethylene HCBr in the CH stretching (v1) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1-40:1) and rotationally assigned to (i) the CH stretch fundamental (v1) band X̃1,0,0←X̃0,0,0 and (ii) vibrational hot bands [X̃(1,1,0)←X̃(0,1,0) and X̃(1,0,1)←X̃(0,0,1)] arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H-C-Br bend (v2) or C-Br stretch (v3) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm-1) in good agreement with previous low-resolution fluorescence studies [M. Deselnicu et al., J. Chem. Phys. 124(13), 134302 (2006)]. Detailed analysis of the fundamental v1 band highlights the presence of perturbations in the X̃1,0,0 level, which we tentatively attribute to arise from the nearby triplet state ã(0,0,1) through spin-orbit interaction or the multiple quanta X̃0,2,1 singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits for clear observation of a nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies [C. Duan et al., J. Mol. Spectrosc. 220(1), 113-121 (2003)]. Finally, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than that predicted by using a bond-dipole model, which from high level ab initio quantum calculations [CCSD(T)/PVQZ] can be attributed to vibrationally induced "charge-sloshing" of electron density along the polar C-Br bond.

High-resolution infrared spectroscopy of jet cooled CH2Br radicals: The symmetric CH stretch manifold and absence of nuclear spin cooling.

Direct laser absorption of a slit supersonic discharge expansion provides the first high-resolution spectroscopic results on the symmetric CH stretch excitation (ν1) of the bromomethyl (CH2Br) radical in the ground electronic state. Narrowband (<1 MHz) mid-infrared radiation is produced by difference-frequency generation of two visible laser beams, with the open shell halohydrocarbon radical generated by electron dissociative attachment of CH2Br2 in a discharge and rapidly cooled to Trot = 18 ± 1 K in the subsequent slit-jet supersonic expansion. A rovibrational structure in the radical spectrum is fully resolved, as well as additional splittings due to spin-rotation effects and 79Br/81Br isotopologues in natural abundance. Spectroscopic constants and band origins are determined by fitting the transition frequencies to a non-rigid Watson Hamiltonian, yielding results consistent with a vibrationally averaged planar radical and an unpaired electron in the out-of-plane pπ orbital. Additionally, extensive satellite band structure from a vibrational hot band is observed and analyzed. The hot band data is compared to CFOUR/VPT2 (CCSD(T)cc-pVQZ) ab initio anharmonic predictions of the vibration rotation alpha matrix, which permits unambiguous assignment to CH2 symmetric-stretch excitation built on the singly excited CH2 out-of-plane bending mode (ν1 + ν4 ← ν4). Longitudinal cooling of the Doppler width in the slit-jet expansion geometry also reveals partially resolved hyperfine structure on transitions out of the lowest angular momentum states in excellent agreement with predictions based on microwave studies. High level ab initio MOLPRO calculations [CCSD(T)-f12b/VnZ-f12 (n = 3, 4, CBS)] are also performed with explicitly correlated f12 electron methods for the out-of-plane CH2 bending mode over the halogen series CH2X (X = F, Cl, Br, I), which clearly reveals a non-planar geometry for X = F (with a ΔE ≈ 0.3 kcal/mol barrier) and yet planar equilibrium geometries for X = Cl, Br, and I. Finally, a detailed Boltzmann analysis of the transition intensities provides support for negligible collisional equilibration of the entangled H atom nuclear spin states on the few hundred microsecond time scale and high collision densities of a slit supersonic expansion.

High-resolution infrared spectroscopy of HCF in the CH stretch region.

We present the results from a high-resolution infrared study of jet-cooled singlet monofluorocarbene (HCF) in the CH stretch region near 2600 cm-1. Absorption signals are recorded using near quantum shot noise limited laser absorption methods. The fully resolved absorption spectra of the CH stretch (ν1) fundamental band and a partial progression of transitions of the HCF bend plus CF stretch (ν2 + ν3) combination band are observed and show clear evidence of a strong rovibrational coupling between the ν1Ka ' = 2 and ν2 + ν3Ka ' = 3 manifolds, including the observation of "dark state" transitions. A detailed perturbation analysis of a c-type Coriolis interaction is carried out for these two coupled vibrational states, providing experimental determination of precise rovibrational constants. A combined ground state combination difference fit of the transitions to the ν1 and ν2 + ν3 vibrational states in this study with previously reported LIF Ã(0,0,0) ← X̃(0,0,0) data has been done to increase the accuracy of the ground state rotational constants [M. Kakimoto et al., J. Mol. Spec. 88, 300-310 (1981)]. Moreover, we report, for the first time, hot band (ν1 + ν3 ← ν3) transitions due to vibrationally excited HCF in the CF stretch mode, ν3. The high-resolution results for all vibrational frequencies and rotational constants are in good agreement with and significantly extend the analysis of the rovibrational manifold of HCF. The present ground state and ν3 spectroscopic parameters now permit improved predictions for pure rotational and ν3 fundamental transitions to aid spectral searches for HCF in the laboratory and the interstellar medium.

Fitting an experimental potential energy curve for the 10(0+)[43Π0] electronic state of NaCs.

We present experimentally determined potential energy curves for the 10(0+)[43Π0] electronic state of NaCs. The 10(0+)[43Π0] state exhibits a double-minimum structure, resulting in a distinctive bound-free fluorescence signature. The perturbation facilitated optical-optical double resonance method was used to obtain Doppler-free excitation spectra corresponding to rovibrational transitions to the 10(0+)[43Π0] state. Spectroscopic constants were determined to summarize data belonging to inner well, outer well, and above the barrier regions of the electronic state. The Rydberg-Klein-Rees and inverted perturbation approach methods were used to construct a potential which reproduces the experimental rovibrational energies within a root-mean-square deviation of 2.33 cm-1. An alternative to the pointwise potential approach was also used to determine the potential energy curve by directly fitting an expanded Morse oscillator functional form. Advantages between the two approaches as they apply to double minimum wells are discussed.

Pulse propagation effects in optical 2D Fourier-transform spectroscopy: experiment.

In optical two-dimensional Fourier-transform (2DFT) spectroscopy, understanding how the spectral line shape is affected by pulse propagation in the sample is crucial for an accurate interpretation of spectra. We report an experimental study of pulse propagation effects in 2DFT spectroscopy performed in a dense atomic vapor. The spectral line shape can be dramatically distorted due to high optical density as well as the physical thickness of a sample. The spectral distortion can be partially corrected by using a reference pulse copropagating with the signal combined with appropriate data processing.