The intermolecular potential-energy surface pertaining to the interaction between benzene and N 2 is investigated theoretically and experimentally. Accurate intermolecular interaction energies are evaluated for the benzene-N 2 van der Waals complex using the coupled cluster singles and doubles including connected triples ͓CCSD͑T͔͒ method and the aug-cc-pVDZ basis set extended with a set of 3s3p2d1 f 1g midbond functions. After fitting the energies to an analytic function, the intermolecular

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... ödinger equation is solved to yield energies, rotational constants, and Raman-scattering coefficients for the lowest intermolecular levels of several benzene-N 2 isotopomers. Experimentally, intermolecular Raman spectra of jet-cooled h 6 -and d 6 -benzene-N 2 measured at 0.03 cm Ϫ1 resolution by mass-selective, ionization-detected stimulated Raman spectroscopies are reported. Seven intermolecular bands are assigned for each isotopomer, including transitions involving intermolecular bending and stretching vibrations and internal rotation about the benzene C 6 axis. These Raman data, together with measured rotational constants and binding energies obtained by other groups on benzene-N 2 , agree well with the theoretical results. Such agreement points to the promise of the quantum chemical methodology employed herein in future investigations of larger van der Waals complexes.