DLPNO-MP2 second derivatives for the computation of polarizabilities and NMR shieldings

We present a derivation and efficient implementation of the formally complete analytic second derivatives for domain-based local pair natural orbital order Møller–Plesset perturbation theory (MP2) method, applicable to electric or magnetic field-response properties but not yet harmonic frequencies. also discuss occurrence avoidance numerical instability issues related singular linear equation systems near dependences in projected atomic domains. A series benchmark calculations on medium-sized is performed assess effect approximation calculated nuclear resonance shieldings static dipole polarizabilities. Relative deviations from resolution identity-based MP2 (RI-MP2) reference both are below 0.5% with default truncation thresholds. For large systems, our achieves quadratic effective scaling, more than RI-MP2 starting at 280 correlated electrons, never 5–20 times slower equivalent Hartree–Fock property calculation. The largest calculation here was vancomycin molecule 176 atoms, 542 4700 basis functions took 3.3 days 12 central processing unit cores.