A four-dimensional intermolecular potential energy surface for the carbon dioxide dimer has been computed using the many-body symmetry-adapted perturbation theory (SAPT) and a large 5s3p2d1f basis set including bond functions. The SAPT level applied is approximately equivalent to the supermolecular many-body perturbation theory at the second-order level. An accurate fit to the computed data has been obtained in a form of an angular expansion incorporating the asymptotic coefficients computed ab initio at the level consistent with the applied SAPT theory. A simpler site-site fit has also been developed to facilitate the use of the potential in molecular dynamics and Monte Carlo simulations. The quality of the new potential has been tested by computing the values of the second virial coefficient which agree very well with the experimental data over a wide range of temperatures. Our potential energy surface turns out to be substantially deeper than previous ab initio potentials. The minimum of −484 cm−1 has been found for the slipped parallel geometry at the intermolecular separation R=3.54 Å and a saddle point at −412 cm−1 for the T-shaped configuration and R=4.14 Å. Three minima and two first-order saddle points have been located on the pairwise-additive potential energy surface of the CO2 trimer. The nonplanar structure of C2 symmetry has been found to be 48.8 cm−1 more stable than the cyclic planar form of C3h symmetry, in disagreement with experimental observation. It is suggested that the relative stability of the two isomers cannot be reliably determined by pairwise-additive potential and inclusion of three-body forces is necessary for this purpose.

Nonrelativistic clamped-nuclei energies of interaction between two ground-state hydrogen molecules with intramolecular distances fixed at their average value in the lowest rovibrational state have been computed. The calculations applied the supermolecular coupled-cluster method with single, double, and noniterative triple excitations [CCSD(T)] and very large orbital basis sets-up to augmented quintuple zeta size supplemented with bond functions. The same basis sets were used in symmetry-adapted perturbation theory calculations performed mainly for larger separations to provide an independent check of the supermolecular approach. The contributions beyond CCSD(T) were computed using the full configuration interaction method and basis sets up to augmented triple zeta plus midbond size. All the calculations were followed by extrapolations to complete basis set limits. For two representative points, calculations were also performed using basis sets with the cardinal number increased by one or two. For the same two points, we have also solved the Schrodinger equation directly using four-electron explicitly correlated Gaussian (ECG) functions. These additional calculations allowed us to estimate the uncertainty in the interaction energies used to fit the potential to be about 0.15 K or 0.3% at the minimum of the potential well. This accuracy is about an order of magnitude better than that achieved by earlier potentials for this system. For a near-minimum T-shaped configuration with the center-of-mass distance R=6.4 bohrs, the ECG calculations give the interaction energy of -56.91+/-0.06 K, whereas the orbital calculations in the basis set used for all the points give -56.96+/-0.16 K. The computed points were fitted by an analytic four-dimensional potential function. The uncertainties in the fit relative to the ab initio energies are almost always smaller than the estimated uncertainty in the latter energies. The global minimum of the fit is -57.12 K for the T-shaped configuration at R=6.34 bohrs. The fit was applied to compute the second virial coefficient using a path-integral Monte Carlo approach. The achieved agreement with experiment is substantially better than in any previous work.

A new four-dimensional intermolecular potential energy surface for the H2-CO complex with fixed intramolecular distances of H2 and CO is presented. The symmetry-adapted perturbation theory has been used to calculate the interaction energy. A large basis set of spdfg type has been used including bond functions. An analytical fit of the ab initio potential energy surface has the global minimum of −109.272 cm−1 at the intermolecular separation of 7.76 bohr for the linear geometry with the C atom pointing toward the H2 molecule. This potential has been used to calculate rovibrational energy levels of CO-para-H2 and CO-ortho-D2 complexes. The resulting dissociation energies are 23.709 cm−1 and 30.756 cm−1, respectively. The computed levels have been used to generate the infrared spectrum accompanying the fundamental vibrational excitation of CO. The transition energies predicted agree well with those observed by McKellar [Chem. Phys. Lett. 186, 58 (1991)].

A new four-dimensional intermolecular potential-energy surface for the H(2)-CO complex is presented. The ab initio points have been computed on a five-dimensional grid including the dependence on the H-H separation (the C-O separation was fixed). The surface has then been obtained by averaging over the intramolecular vibration of H(2). The coupled-cluster supermolecular method with single, double, and noniterative triple excitations has been used to calculate the interaction energy. The correlation part of the interaction energy has been obtained from extrapolations based on calculations in a series of basis sets. An analytical fit of the ab initio potential-energy surface has the global minimum of -93.049 cm(-1) at the intermolecular separation of 7.92 bohr for the linear geometry with the C atom pointing toward the H(2) molecule. For the other linear geometry, with the O atom pointing toward H(2), the local minimum of -72.741 cm(-1) has been found for the intermolecular separation of 7.17 bohr. The potential has been used to calculate the rovibrational energy levels of the para-H(2)-CO complex. The results agree very well with those observed by McKellar [A. R. W. McKellar J. Chem. Phys. 108, 1811 (1998)]: the discrepancies are smaller than 0.1 cm(-1). The calculated dissociation energy is equal to 19.527 cm(-1) and significantly smaller than the value of 22 cm(-1) estimated from the experiment. Predictions of rovibrational energy levels for ortho-H(2)-CO have also been done and can serve as a guidance to assign recorded experimental spectra. The interaction second virial coefficient has been calculated and compared with the experimental data.