Flesch R, Pavlychev A A, Neville J J, Blumberg J, Kuhlmann M, Tappe W, Senf F, Schwarzkopf O, Hitchcock A P, Rühl E
Fachbereich Physik, Universität, Osnabrück, Barbarastrasse 7, 49069 Osnabrück, Germany.
Phys Rev Lett. 2001 Apr 23;86(17):3767-70. doi: 10.1103/PhysRevLett.86.3767.
High-resolution 1s near-edge spectra of molecular nitrogen and variable size nitrogen clusters obtained using monochromatic synchrotron radiation from the high brilliance BESSY-II storage ring facility are reported. The vibrationally resolved 1sigma(u)-->1pi(g) core-to-valence excitation band of clusters shows a distinct redshift of 6+/-1 meV relative to the isolated molecule, but the vibrational structure and linewidths are essentially unchanged. This shift is assigned to dynamic stabilization of 1sigma(u)-->1pi(g) excited molecules in clusters, arising from the dynamic dipole moment generated by core-hole localization in the low-symmetry cluster field. This leads to changes in intermolecular interactions compared to the ground-state cluster. Such spectral shifts are expected to occur generally in molecular clusters and in the corresponding condensed phase.
报道了使用来自高亮度BESSY-II储存环设施的单色同步辐射获得的分子氮和可变尺寸氮团簇的高分辨率1s近边光谱。团簇的振动分辨1σ(u)→1π(g)芯到价激发带相对于孤立分子显示出6±1 meV的明显红移,但振动结构和线宽基本不变。这种位移归因于团簇中1σ(u)→1π(g)激发分子的动态稳定化,这是由低对称团簇场中芯孔局域化产生的动态偶极矩引起的。与基态团簇相比,这导致分子间相互作用发生变化。预计这种光谱位移通常会在分子团簇和相应的凝聚相中出现。