Institute for Physical and Theoretical Chemistry, University of Regensburg, Germany.
Phys Chem Chem Phys. 2023 Jan 27;25(4):3287-3297. doi: 10.1039/d2cp04514a.
Clusters consisting of a single phthalocyanine molecule and a single water molecule are investigated by means of electronic spectroscopy in superfluid helium droplets. A recent spectroscopic study of those clusters [J. Fischer, F. Schlaghaufer, E.-M. Lottner, A. Slenczka, L. Christiansen, H. Stapelfeldt, M. Karra, B. Friedrich, T. Mullan, M. Schütz and D. Usvyat, , 2019, , 10057-10064] which all exhibit a water induced electronic shift to the red is now complemented by the corresponding clusters exhibiting a water induced shift to the blue. These clusters will be analyzed by means of fluorescence excitation spectra, dispersed emission spectra, and additional experimental observations made feasible by helium droplets as cryogenic reactor. Together with the blue shifted clusters a total number of at least 6 isomeric variants could be identified in helium droplets. This contrasts to a number of only three isomeric variants obtained from quantum chemical calculations [J. Fischer, F. Schlaghaufer, E.-M. Lottner, A. Slenczka, L. Christiansen, H. Stapelfeldt, M. Karra, B. Friedrich, T. Mullan, M. Schütz and D. Usvyat, , 2019, , 10057-10064] disregarding the helium environment and to a single isomer identified in a molecular beam experiment [J. Menapace and E. Bernstein, , 1987, , 6877-6889]. The discrepancy in the number of isomers provides evidence of a profound involvement of helium in clustering. Moreover, the discrepancies between the gas phase experiment and quantum chemical calculations similarly reveal the influence of the dynamics of cluster formation on the population of global and local minima that are accessible as isomeric variants.
在氦超流体液滴中通过电子光谱学研究了由单个酞菁分子和单个水分子组成的团簇。最近对这些团簇的光谱研究[J. Fischer、F. Schlaghaufer、E.-M. Lottner、A. Slenczka、L. Christiansen、H. Stapelfeldt、M. Karra、B. Friedrich、T. Mullan、M. Schütz 和 D. Usvyat，2019，10057-10064]表明，所有显示出由于水分子引起的电子向红色移动的团簇，现在都被相应的显示出由于水分子引起的向蓝色移动的团簇所补充。这些团簇将通过荧光激发光谱、分散发射光谱以及通过氦液滴作为低温反应堆实现的其他实验观察来进行分析。与从量子化学计算中获得的只有三种异构体变体的数量相比[J. Fischer、F. Schlaghaufer、E.-M. Lottner、A. Slenczka、L. Christiansen、H. Stapelfeldt、M. Karra、B. Friedrich、T. Mullan、M. Schütz 和 D. Usvyat，2019，10057-10064]，不计氦环境的影响，并且与分子束实验中鉴定的单个异构体[J. Menapace 和 E. Bernstein，1987，6877-6889]相比，在氦液滴中可以识别出至少 6 种异构体变体。异构体数量的差异为氦在成簇过程中的深入参与提供了证据。此外，气相实验与量子化学计算之间的差异同样揭示了成簇动力学对可作为异构体变体的全局和局部最小值的分布的影响。
