The dispersion energies, induction energies and their exchange counterparts (exchange-dispersion and ex-change-induction energies) between two interacting nitramide molecules at several separations are derived based u...The dispersion energies, induction energies and their exchange counterparts (exchange-dispersion and ex-change-induction energies) between two interacting nitramide molecules at several separations are derived based upon symmetry-adapted perturbation theory (SAPT). The results show that (1) the effect of intramonomer electron correlation on dispersion energies and induction energies for nitramide dimer system is remarkable especially in the region near the van der Waals minimum distance (0.42 nm). (2) At smaller separations the dispersion energies and the induction energies are largely quenched by their exchange counterparts, and this case in induction interaction is much more remarkable than in dispersion interaction. (3) Since at shorter distances there exists the strong short-range interaction due to electron transfer which quickly decays and even disappears at larger separations, the two different R-dependency formulae of induction energies were found: one is ca. R-12.7 at short distances, and the other ca. R-7.0 at large separations. The latter R-dependency is similar to that (ca. R-7.2) of dispersion. (4) In the case of strong polar interaction existing in nitramide dimer, the true induction correlation terms of higher order than t(22)indE may be important.展开更多
基金Project supported by the Fund of Institute of Chemical Materials (Grant No. 42105080107) the National Natural Science Foundation of China (Grant Nos. 10176012 20173028) and the fund of China Academy of Engineering Physics (Grant No. 2002Z0501).
文摘The dispersion energies, induction energies and their exchange counterparts (exchange-dispersion and ex-change-induction energies) between two interacting nitramide molecules at several separations are derived based upon symmetry-adapted perturbation theory (SAPT). The results show that (1) the effect of intramonomer electron correlation on dispersion energies and induction energies for nitramide dimer system is remarkable especially in the region near the van der Waals minimum distance (0.42 nm). (2) At smaller separations the dispersion energies and the induction energies are largely quenched by their exchange counterparts, and this case in induction interaction is much more remarkable than in dispersion interaction. (3) Since at shorter distances there exists the strong short-range interaction due to electron transfer which quickly decays and even disappears at larger separations, the two different R-dependency formulae of induction energies were found: one is ca. R-12.7 at short distances, and the other ca. R-7.0 at large separations. The latter R-dependency is similar to that (ca. R-7.2) of dispersion. (4) In the case of strong polar interaction existing in nitramide dimer, the true induction correlation terms of higher order than t(22)indE may be important.
