Ab initio potential and rotational spectra of the CO-N2 complex.

Ab initio calculations of the intermolecular potential energy surface (PES) of CO-N2 have been carried out using the closed-shell single- and double-excitation coupled cluster approach with a non-iterative perturbative treatment of triple excitations method and the augmented correlation-consistent quadruple-zeta (aug-cc-pVQZ) basis set supplemented with midbond functions. The global minimum (De = 117.35 cm-1) of the four-dimensional PES corresponds to an approximately T-shaped structure with the N2 subunit forming the leg and CO the top. The bound rovibrational levels of the CO-N2 complex were calculated for total angular momenta J = 0-8 on this intermolecular potential surface. The calculated dissociation energies D0 are 75.60 and 76.79 cm-1 for the ortho-N2 (A-symmetry) and para-N2 (B-symmetry) nuclear spin modifications of CO-N2, respectively. Guided by these bound state calculations, a new millimeter-wave survey for the CO-N2 complex in the frequency range of 110-145 GHz was performed using the intracavity OROTRON jet spectrometer. Transitions not previously observed were detected and assigned to the subbands connecting the K = 0 and 1, (jCO, jN2 ) = (1, 0) states with a new K = 1, (jCO, jN2 ) = (2, 0) state. Finally, the measured rotational energy levels of the CO-N2 complex were compared to the theoretical bound state results, thus providing a critical test of the quality of the PES presented. The computed rovibrational wave functions were analyzed to characterize the nature of the different bound states observed for the two nuclear spin species of CO-N2.

Rotational study of the CH4-CO complex: Millimeter-wave measurements and ab initio calculations.

The rotational spectrum of the van der Waals complex CH4-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110-145 GHz. Newly observed and assigned transitions belong to the K = 2-1 subband correlating with the rotationless jCH4 = 0 ground state and the K = 2-1 and K = 0-1 subbands correlating with the jCH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH4-CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4-CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH4 face closest to the CO subunit and binding energy De = 177.82 cm(-1). The bound rovibrational levels of the CH4-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 91.32, 94.46, and 104.21 cm(-1) for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4-CO, respectively.

Rotational study of the NH3-CO complex: millimeter-wave measurements and ab initio calculations.

The rotational spectrum of the van der Waals complex NH3-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 112-139 GHz. Newly observed and assigned transitions belong to the K = 0-0, K = 1-1, K = 1-0, and K = 2-1 subbands correlating with the rotationless (jk)NH3 = 00 ground state of free ortho-NH3 and the K = 0-1 and K = 2-1 subbands correlating with the (jk)NH3 = 11 ground state of free para-NH3. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. Some of these transitions are continuations to higher J values of transition series observed previously [C. Xia et al., Mol. Phys. 99, 643 (2001)], the other transitions constitute newly detected subbands. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the ortho-NH3-CO and para-NH3-CO complexes. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of NH3-CO has been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations and an augmented correlation-consistent triple zeta basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the N atom closest to the CO subunit and binding energy De = 359.21 cm(-1). The bound rovibrational levels of the NH3-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 210.43 and 218.66 cm(-1) for ortho-NH3-CO and para-NH3-CO, respectively.

A comprehensive experimental and theoretical study of H2-CO spectra.

A detailed description of a new ab initio interaction potential energy surfaces for the H2-CO complex computed on a six-dimensional grid (i.e., including the dependence on the H-H and C-O separations) is presented. The interaction energies were first calculated using the coupled-cluster method with single, double, and noniterative triple excitations and large basis sets, followed by an extrapolation procedure. Next, a contribution from iterative triple and noniterative quadruple excitations was added from calculations in smaller basis sets. The resulting interaction energies were then averaged over the ground-state and both ground- and first-excited-states vibrational wave functions of H2 and CO, respectively. The two resulting four-dimensional potential energy surfaces were fitted by analytic expressions. Theoretical infrared spectra calculated from these surfaces have already been shown [P. Jankowski, A. R. W. McKellar, and K. Szalewicz, Science 336, 1147 (2012)] to agree extremely well, to within a few hundredth of wavenumber, with the experimental spectra of the para and orthoH2-CO complex. In the latter case, this agreement enabled an assignment of the experimental spectrum, ten years after it had been measured. In the present paper, we provide details concerning the development of the surfaces and the process of spectral line assignment. Furthermore, we assign some transitions for paraH2-CO that have not been assigned earlier. A completely new element of the present work are experimental investigations of the orthoH2-CO complex using microwave spectroscopy. Vast parts of the measured spectrum have been interpreted by comparisons with the infrared experiments, including new low-temperature ones, and theoretical spectrum. Better understanding of the spectra of both para and orthoH2-CO complexes provides a solid foundation for a new search of the bound H2-CO complex in space.

Rotational study of carbon monoxide isotopologues in small (4)He clusters.

High resolution microwave (a-type) and millimetre-wave (b-type) spectra of He(N)-(13)C(16)O, He(N)-(12)C(18)O, and He(N)-(13)C(18)O clusters (N

Rotational study of carbon monoxide solvated with helium atoms.

High resolution microwave and millimeter-wave spectra of HeN-CO clusters with N up to 10, produced in a molecular expansion, were observed. Two series of J = 1-0 transitions were detected, which correspond to the a-type and b-type J = 1-0 transitions of He1-CO. The B rotational constant initially decreases with N and reaches a minimum at N = 3. Its subsequent rise indicates the transition from a molecular complex to a quantum solvated system already for N = 4. For N > or =6, the B value becomes larger than that of He1-CO, indicating an almost free rotation of CO within the helium environment.

Isotope effects in the CO dimer: millimeter wave spectrum and rovibrational calculations of (12C18O)2.

The millimeter wave spectrum of the isotopically substituted CO dimer, (12C18O)2, was studied with the Orotron jet spectrometer, confirming and extending a previous infrared study [A. R. W. McKellar, J. Mol. Spectrosc. 226, 190 (2004)]. A very dilute gas mixture of CO in Ne was used, which resulted in small consumption of 12C18O sample gas and produced cold and simple spectra. Using the technique of combination differences together with the data from the infrared work, six transitions in the 84-127 GHz region have been assigned. They belong to two branches, which connect four low levels of A+ symmetry to three previously unknown levels of A- symmetry. The discovery of the lowest state of A- symmetry, which corresponds to the projection K=0 of the total angular momentum J onto the intermolecular axis, identifies the geared bending mode of the 12C18O dimer at 3.607 cm(-1). Accompanying rovibrational calculations using a recently developed hybrid potential from ab initio coupled cluster [CCSD(T)] and symmetry-adapted perturbation theory calculations [G. W. M. Vissers et al., J. Chem. Phys. 122, 054306 (2005)] gave very good agreement with experiment. The isotopic dependence of the A+/A- energy splitting, the intermolecular separation R, and the energy difference of two ground state isomers, which change significantly when 18O or 13C are substituted into the normal (12C16O)2 isotopolog [L. A. Surin et al., J. Mol. Spectrosc. 223, 132 (2004)], was explained by these calculations. It turns out that the change in anisotropy of the intermolecular potential with respect to the shifted monomer centers of mass is particularly significant.

Doppler-free two-photon millimeter wave transitions in OCS and CHF3.

Doppler-free two-photon rotational transitions J = 13<--<--11 and J = 12<--<--10 of OCS and J = 8<--<--6 and J = 7<--<--5 of CHF (3) were detected in the frequency range 134-156 GHz, using a novel, highly sensitive intracavity-jet technique. The sub-Doppler narrowing of the observed peaks (down to 40 kHz full width at half maximum as compared to 300 kHz of the Doppler width) demonstrates the potential of this new technique for high precision millimeter wave spectroscopy. The possibilities of the further reduction of the two-photon absorption line widths are considered.