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We evaluate the shifts imparted to vibrational and rotational levels of alinear molecule by a nonresonant laser field at intensities of up to 10^12W/cm^2. Both types of shift are found to be either positive or negative,depending on the initial rotational state acted upon by the field. An adiabaticfield-molecule interaction imparts a rotational energy shift which is negativeand exceeds the concomitant positive vibrational shift by a few orders ofmagnitude. The rovibrational states are thus pushed downward in such a field. Anonresonant pulsed laser field that interacts nonadiabatically with themolecule is found to impart rotational and vibrational shifts of the same orderof magnitude. The nonadiabatic energy transfer occurs most readily at a pulseduration which amounts to about a tenth of the molecule's rotational period,and vanishes when the sudden regime is attained for shorter pulses. We appliedour treatment to the much studied 87Rb_2 molecule in the last bound vibrationallevels of its lowest singlet and triplet electronic states. Our calculationsindicate that 15 ns and 1.5 ns laser pulses of an intensity in excess of 5x10^9W/cm^2 are capable of dissociating the molecule due to the vibrational shift.Lesser shifts can be used to fine tune the rovibrational levels and thereby toaffect collisional resonances by the nonresonant light. The energy shifts maybe discernible spectroscopically, at a 10 MHz resolution.

Fine-tuning molecular energy levels by nonresonant laser pulses