How Does a Solvent Affect Chemical Bonds? Mixed Quantum/Classical Simulations with a Full CI Treatment of the Bonding Electrons

作者：Glover William J; Larsen Ross E; Schwartz Benjamin J^*

来源：Journal of Physical Chemistry Letters, 2010, 1(1): 165-169.

DOI：10.1021/jz9000938

Understanding how a solvent affects the quantum mechanics and reactivity of the chemical bonds of dissolved solutes is of fundamental importance to chemistry. TO explore condensed-phase effects on a simple molecular solute, we have studied the,six-dimensional two-electron wave function of the bonding electrons of the Na(2) molecule in liquid argon via mixed quantum/classical simulation. We find that even though Ar is an apolar liquid, solvent interactions produce dipole moments on Na(2) that can reach magnitudes over 1.4 D. These interactions also change the selection rules, induce significant motional-narrowing, and cause a large (26 cm(-1)) blue shift of the dimer's vibrational spectrum relative to that in the gas phase. These effects cannot be captured via classical simulation, highlighting the importance of quantum many-body effects.

• 出版日期2010-1