Structural characterization of the NO(X2Π)-N2O complex with mid-infrared laser absorption spectroscopy and quantum chemical calculations.

Both positive and negative ions of N3O2 have been observed in various experiments. The neutral N3O2 was predicted to exist either as a weakly bound NO·N2O complex or a covalent molecule. The rovibrational spectrum of the NO(X2Π)-N2O complex has been measured for the first time in the 5.3 µm region using distributed quantum cascade lasers to probe the direct absorption in a slit-jet supersonic expansion. The observed spectrum is analyzed with a semi-rigid asymmetric rotor Hamiltonian for a planar open-shell complex, giving a bent geometry with an a-axis-NO angle of about 21.9°. The vibrationally averaged 2A'-2A″ energy separation is determined to be ε = 144.56(95) cm-1 for the ground state, indicating that the electronic orbital angular momentum is partially quenched upon complexation. Geometry optimizations of the complex restricted to a planar configuration at the RCCSD(T)/aug-cc-pVTZ level of theory show that the 2A″ state is more stable than the 2A' state by about 110 cm-1 and the N atom of NO points to the central N atom of N2O at the minimum of the 2A″ state.

Mid-infrared quantum cascade laser spectroscopy of the Ar-NO complex: Fine and hyperfine structure.

The rovibrational spectrum of the Ar-NO open-shell complex has been measured in the 5.3 µm region using distributed feed-back quantum lasers to probe the direct absorption in a slit-jet supersonic expansion. Five P-subbands, namely, P'←P″:1/2←3/2,1/2←1/2,3/2←1/2,5/2←3/2, and 7/2←5/2, are observed, with J up to 15.5. The hyperfine structure due to the nuclei spin of 14N (I = 1) can be partially resolved in the P'←P″:1/2←3/2,1/2←1/2, and 3/2←1/2 subbands. The fine structure of the observed spectrum is analyzed using a modified semi-rigid rotor Hamiltonian [W. M. Fawzy and J. T. Hougen, J. Mol. Spectrosc. 137, 154-165 (1989)] and an empirical Hamiltonian [Y. Kim and H. Meyer, Int. Rev. Phys. Chem. 20, 219-282 (2001)] separately. The hyperfine structure can be simulated successfully by including hyperfine terms to the semi-rigid rotor Hamiltonian. A linear J-dependence of the angle between the inertial a-axis of the complex and the intramolecular axis of the NO subunit is also introduced in order to model the strong structure relaxation effect in the P = 1/2 state.

Mid-infrared laser absorption spectroscopy of the Ne-NO(X2Π) complex.

The rovibrational spectrum of the Ne-NO(X2Π) open-shell complex has been measured in the 5.3 µm region using distributed feed-back quantum cascade lasers to probe the direct absorption in a slit-jet supersonic expansion. Three P-subbands (P' ← P″: 1/2 ← 1/2, 3/2 ← 1/2, and 5/2 ← 3/2) were observed, where P is the projection of the angular momentum J along the inertial a-axis of the complex. The hyperfine structure due to the nuclei spin of 14N (I = 1) was partially resolved in the P' ← P″: 1/2 ← 1/2 and 3/2 ← 1/2 subbands. The observed mid-infrared spectrum of Ne-NO (X2Π) together with the previously reported microwave spectrum was analyzed using a modified semirigid asymmetric rotor Hamiltonian for a planar open-shell complex. The band origin is located at 1876.0606(97) cm-1, which is blue-shifted from that of the NO monomer by only 0.0888 cm-1. The complex shows strong structural relaxation upon excitation of the overall rotation and the internal rotation of the NO subunit.

High resolution jet-cooled infrared absorption spectra of (HCOOH)2, (HCOOD)2, and HCOOH-HCOOD complexes in 7.2 µm region.

The rotationally resolved infrared spectra of (HCOOH)2, (HCOOD)2, and HCOOH-HCOOD complexes have been measured in 7.2 µm region by using a segmented rapid-scan distributed-feedback quantum cascade laser absorption spectrometer to probe a slit supersonic jet expansion. The observed spectra are assigned to the v21 (H-C/O-H in-plane bending) fundamental band of (HCOOH)2, the v15 (H-C/O-D in-plane bending) fundamental band of HCOOH-HCOOD, and the v20 (H-C-O in-plane bending) fundamental band of (HCOOD)2. Strong local perturbations caused by the rotation-tunneling coupling between two tunneling components are observed in (HCOOH)2. The v21 fundamental band of (HCOOH)2 and the previously measured v22 fundamental and v12 + v14 combination bands [K. G. Goroya et al., J. Chem. Phys. 140, 164311 (2014)] are analyzed together, yielding a more precise tunneling splitting in the ground state, 0.011 367(92) cm-1. The band-origin of the v21 band of (HCOOH)2 is 1371.776 74(8) cm-1, and the tunneling splitting decreases to 0.000 38(18) cm-1 upon the vibrational excitation. The vibrational energy is 1386.755 49(16) cm-1 for the v15 vibrational mode of HCOOH-HCOOD and 1391.084 39(17) cm-1 for the v20 vibrational mode of (HCOOD)2. No apparent spectral splittings are resolved for HCOOH-HCOOD and (HCOOD)2 under our experimental conditions. The tunneling splitting in the ground state of HCOOH-HCOOD is estimated to be 0.001 13 cm-1 from its average linewidth.

High resolution jet-cooled infrared absorption spectra of the formic acid dimer: a reinvestigation of the C-O stretch region.

The vibration-rotation-tunneling absorption spectra of the formic acid dimer (HCOOH)2 have been measured in the C-O stretch region at 1215-1240 cm(-1) using a rapid-scan tunable diode laser spectrometer in conjunction with a slit supersonic expansion. The ν5 fundamental band of the HCOOH monomer is identified and the perturbed band-center is 1220.83329(10) cm(-1). Three vibrational bands centered at 1219.71, 1225.35, and 1233.95 cm(-1) are assigned to the two combination bands and the ν22 fundamental band of (HCOOH)2 unambiguously. The transition frequencies of these three vibrational bands are fitted together using a standard Watson A-reduced Hamiltonian, yielding precise rotational and centrifugal distortion constants for each tunneling level in the ground and excited vibrational states. The fitting results of the vibrational band centered at 1225.35 cm(-1) are in good agreement with a previous high resolution study [M. Ortlieb and M. Havenith, J. Phys. Chem. A. 111, 7355 (2007)]. The tunneling splittings in the vibrationally excited states are -0.00304(16), -0.01023(11), and -0.00318(12) cm(-1), respectively, where the minus indicates that the upper tunneling component lies energetically below the lower tunneling component. A three-state deperturbation analysis using the Fermi coupling constants obtained from a previous vibrational analysis [F. Ito, Chem. Phys. Lett. 447, 202 (2007)] fails to get the normal order of the tunneling levels for all the three excited vibrational states simultaneously.

Theoretical prediction of the linear isomers for rare gas-carbon disulfide complexes: He-CS2, Ne-CS2, and Ar-CS2.

Theoretical studies of the potential energy surfaces (PESs) and bound states are performed for rare gas-carbon disulfide complexes, He-CS2, Ne-CS2, and Ar-CS2. Three two-dimensional intermolecular PESs are constructed from ab initio data points which are calculated at the CCSD(T) level with aug-cc-pVTZ basis set supplemented with bond functions. We find that the three PESs have very similar features and each PES can be characterized by a global T-shaped minimum, two equivalent local linear minima, and the saddle points between them. The T-shaped isomer is energetically more stable than the linear isomer for each complex. The linear isomers, which have not been observed in experiment so far, are predicted from our PESs and further identified by bound state calculations. Moreover, we assign several intermolecular vibrational states for both the T-shaped and linear isomers of the three complexes via the analysis of wavefunctions. The corresponding vibrational frequencies are calculated from the bound state energies for these assigned states. These frequencies could be helpful for further experimental studies, especially for the linear isomers. We also calculate the rovibrational transition frequencies for the three T-shaped isomers and the pure rotational transition frequencies for the linear isomers, respectively. The accuracy of the PESs is validated by the good agreement between theoretical and experimental results for the rovibrational transition frequencies and spectroscopic parameters.

Infrared spectra and tunneling dynamics of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O.

The rovibrational spectra of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O have been measured in a supersonic slit jet expansion using a rapid-scan tunable diode laser spectrometer. Both a-type and b-type transitions were observed for these two complexes. All transitions are doubled, due to the heavy water tunneling within the complexes. Assuming the tunneling splittings are the same in K(a) = 0 and K(a) = 1, the band origins, all three rotational and several distortion constants of each tunneling state were determined for N2-D2O in the ground and excited vibrational states, and for OC-D2O in the excited vibrational state, respectively. The averaged band origin of OC-D2O is blueshifted by 2.241 cm(-1) from that of the v2 band of the D2O monomer, compared with 1.247 cm(-1) for N2-D2O. The tunneling splitting of N2-D2O in the ground state is 0.16359(28) cm(-1), which is about five times that of OC-D2O. The tunneling splittings decrease by about 26% for N2-D2O and 23% for OC-D2O, respectively, upon excitation of the D2O bending vibration, indicating an increase of the tunneling barrier in the excited vibrational state. The tunneling splittings are found to have a strong dependence on intramolecular vibrational excitation as well as a weak dependence on quantum number K(a).

Mid-infrared Laser Spectroscopy of Jet-Cooled Formic Acid Trimer: Mode-Dependent Line Broadening in the C-O Stretching Region.

Building on recent progress in the vibrational spectroscopy of the formic acid trimer, we present the first high-resolution measurements of the jet-cooled laser absorption spectrum of (HCOOH)3. The spectra of the lowest- and highest-frequency C-O stretching fundamentals are analyzed whereas the third band is not observed, complicated by monomer and dimer absorptions at 1219 cm-1 (8.2 µm). Vibration-rotation parameters are obtained for the band at 1172.31512(68) cm-1 whereas the C-O stretch at 1246.33(5) cm-1 exhibits a significantly larger breadth, allowing only resolution of the coarse PQR structure. Vibrational predissociation can be ruled out, and intramolecular vibrational redistribution mechanisms are discussed, particularly coupling to the concerted proton exchange within the cyclic dimer subunit. Ultimately, the question remains open. The prospects of high-resolution measurements of other trimer bands or isotope substitution experiments, which might assist in revealing the mode-specificity of the underlying broadening mechanisms, are discussed.

Infrared diode laser spectroscopy of the Ne-D2O van der Waals complex: strong Coriolis and angular-radial coupling.

Four internal-rotation/vibration bands of the Ne-D(2)O complex have been measured in the v(2) bend region of D(2)O using a tunable infrared diode laser spectrometer to probe a slit supersonic expansion. Three ortho bands are excited from the ground state Σ(0(00)) to the Σ and Π(1(11), υ(2) = 1) internal rotor states and the n = 1, Σ(0(00), υ(2) = 1) stretching-internal rotor combination state. Strong perturbations between the excited vibrational states are evident. The observed spectra are analyzed separately with a three-state J-dependent Coriolis plus J-independent angular-radial coupling model [M. J. Weida and D. J. Nesbitt, J. Chem. Phys. 106, 3078 (1997)] and a three-state Coriolis coupling model [R. C. Cohen and R. J. Saykally, J. Chem. Phys. 95, 7891 (1991)]. The former model works more successfully than the latter. Molecular constants for the ground and excited vibrational states of ortho (20)Ne-D(2)O isotopomer as well as the Coriolis and angular-radial coupling constants are determined accurately. The van der Waals stretching frequency is estimated to be ν(s) = 24.85 cm(-1) in the ground state and decreases to about 20.8 cm(-1) upon vibrational excitation of the D(2)O bend.