Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
Laboratorium für Physikalische Chemie, ETH Zürich , Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland.
J Chem Theory Comput. 2017 Aug 8;13(8):3764-3777. doi: 10.1021/acs.jctc.7b00329. Epub 2017 Jul 25.
Variational approaches for the calculation of vibrational wave functions and energies are a natural route to obtain highly accurate results with controllable errors. Here, we demonstrate how the density matrix renormalization group (DMRG) can be exploited to optimize vibrational wave functions (vDMRG) expressed as matrix product states. We study the convergence of these calculations with respect to the size of the local basis of each mode, the number of renormalized block states, and the number of DMRG sweeps required. We demonstrate the high accuracy achieved by vDMRG for small molecules that were intensively studied in the literature. We then proceed to show that the complete fingerprint region of the sarcosyn-glycin dipeptide can be calculated with vDMRG.
变分方法是计算振动波函数和能量的一种自然途径，可以获得具有可控误差的高度精确结果。在这里，我们展示了如何利用密度矩阵重整化群（DMRG）来优化以矩阵乘积态表示的振动波函数（vDMRG）。我们研究了这些计算在每个模式的局部基大小、正则化块态数量以及所需的 DMRG 扫数方面的收敛性。我们展示了 vDMRG 在文献中被深入研究的小分子中所达到的高精度。然后，我们继续展示 vDMRG 可以计算sarcosyn-甘氨酸二肽的完整指纹区域。
