The University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
The University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom and Theory and Simulation of Condensed Matter, King's College London, Strand, London WC2 R 2LS, United Kingdom.
Phys Rev Lett. 2015 Jan 23;114(3):033001. doi: 10.1103/PhysRevLett.114.033001. Epub 2015 Jan 21.
Accurate ionization potentials of the first-row transition-metal atoms are obtained via the initiator full configuration quantum Monte Carlo technique, performing a stochastic integration of the electronic Schrödinger equation in exponentially large Hilbert spaces, with a mean absolute error of 0.13 kcal/mol (5 meV). This accuracy requires correlation of the 3p semicore electrons and in some cases the 3s manifold, along with extrapolation of the correlation energies to the complete-basis-set limit, and provides a new theoretical benchmark for the ionization potentials of these systems.
通过引发剂全组态量子蒙特卡罗技术，获得了第一行过渡金属原子的精确电离势，该技术在指数级大的 Hilbert 空间中对电子薛定谔方程进行随机积分，平均绝对误差为 0.13 千卡/摩尔（5 毫电子伏特）。这种精度要求 3p 半芯电子以及在某些情况下 3s 态的相关，同时需要将相关能量外推到完全基组极限，为这些体系的电离势提供了新的理论基准。
