Pair Natural Orbitals for Coupled Cluster Quadratic Response Theory
Jose P. Madriaga, Monika Kodrycka, T. Daniel Crawford
TL;DR
This paper explores how using pair natural orbitals can improve the efficiency of quantum chemistry calculations for large molecules.
Contribution
The paper introduces and evaluates new methods combining pair natural orbitals with response property optimizations for coupled cluster calculations.
Findings
PNO++ methods improve accuracy in response properties compared to standard PNOs.
Combined-PNO++ maintains CCSD correlation energy accuracy while reducing computational cost.
Truncation errors were analyzed using electric dipole hyperpolarizability metrics.
Abstract
Reduced-scaling approaches have yielded significant improvements in the computational efficiency of coupled cluster methods, making them more feasible for studying large molecules. In this work, we extend the use of pair natural orbitals (PNOs) to frequency-dependent quadratic response properties. We evaluate the performance of PNOs alongside methods optimized for response properties that derive from an approximate field-perturbed density matrix known as perturbation-aware PNOs (PNO++). Additionally, we concatenate the PNO and PNO++ spaces to obtain the combined-PNO++ method, which is tailored to simultaneously maintain the accuracy of the CCSD correlation energies and response properties. We analyze the truncation errors associated with these methods using first electric dipole hyperpolarizability – specifically the average second-harmonic generation and optical refractivity, using…
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Taxonomy
TopicsMolecular spectroscopy and chirality · Synthesis and Properties of Aromatic Compounds · Spectroscopy and Quantum Chemical Studies