Anomalous light-induced drift of linear molecules

The sudden approximation in energy is used to derive analytic formulas that describe the anomalous light-induced drift (LID) of linear molecules absorbing radiation in the rovibrational transition nJ _i −mJ _f (n and m are the ground and excited vibrational states, and J _α is the rotational quantum number in the vibrational state α=m, n). It is shown that for all linear molecules with moderate values B≲1 cm⁻¹ of the rotational constant, anomalous LID can always by observed under the proper experimental conditions; temperature T, rotational quantum number J _i , and type of transition (P or R). The parameter γ=BJ _i (J _i +1)−J _f (J _f +1)] ν _n /2k _BT (ν _m −ν _n ) is used to derive a condition for observing anomalous LID: γ∼1 (k _B is the Boltzmann constant and ν _α is the transport rate of collisions of molecules in the vibrational state α and buffer particles at moderate molecular velocities , where is the most probable velocity of the buffer particles). For ν _m >ν _n anomalous LID can be observed only in P-transitions, while for ν _m <ν _n it can be observed only in R-transitions. It is shown that anomalous LID is possible for all ratios β=M _b /M of the masses of the buffer particles (M _b ) and of the resonant particles (M) and any absorption-line broadening (Doppler or homogeneous). The optimum conditions for observing anomalous LID are realized when the absorption line is Doppler-broadened in an atmosphere of medium-weight (β∼1) and heavy (β≫1) buffer particles. In this case, anomalous LID can be observed in the same transition within a broad temperature interval ΔT∼T. If the buffer particles are light (β≪1) or if the broadening of the absorption line is homogeneous, anomalous LID in the same transition can be observed only within a narrow temperature range ΔT≪T. Zh. éksp. Teor. Fiz. 115, 1664–1679 (May 1999)