Convergence Acceleration of Parallel Monte Carlo Second-Order Many-Body Perturbation Calculations Using Redundant Walkers

2013 ◽  
Vol 9 (10) ◽  
pp. 4396-4402 ◽  
Author(s):  
Soohaeng Yoo Willow ◽  
Matthew R. Hermes ◽  
Kwang S. Kim ◽  
So Hirata
Keyword(s):  
Monte Carlo ◽  
Convergence Acceleration ◽  
Second Order ◽  
Many Body

scholarly journals Monte Carlo explicitly correlated second-order many-body perturbation theory

2016 ◽  
Vol 145 (15) ◽  
pp. 154115 ◽  
Author(s):  
Cole M. Johnson ◽  
Alexander E. Doran ◽  
Jinmei Zhang ◽  
Edward F. Valeev ◽  
So Hirata
Keyword(s):  
Monte Carlo ◽  
Perturbation Theory ◽  
Second Order ◽  
Many Body ◽  
Explicitly Correlated ◽  
Many Body Perturbation Theory

Divergence of Many-Body Perturbation Theory for Noncovalent Interactions of Large Molecules

2019 ◽  
Author(s):  
Brian Nguyen ◽  
Guo P Chen ◽  
Matthew M. Agee ◽  
Asbjörn M. Burow ◽  
Matthew Tang ◽  
...  
Keyword(s):  
Perturbation Theory ◽  
System Size ◽  
State Density ◽  
Second Order ◽  
Binding Energies ◽  
Basis Set ◽  
Many Body ◽  
Many Body Perturbation Theory ◽  
Relative Errors ◽  
Ground State Density

Prompted by recent reports of large errors in noncovalent interaction (NI) energies obtained from many-body perturbation theory (MBPT), we compare the performance of second-order Møller–Plesset MBPT (MP2), spin-scaled MP2, dispersion-corrected semilocal density functional approximations (DFA), and the post-Kohn–Sham random phase approximation (RPA) for predicting binding energies of supramolecular complexes contained in the S66, L7, and S30L benchmarks. All binding energies are extrapolated to the basis set limit, corrected for basis set superposition errors, and compared to reference results of the domain-based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) or better quality. Our results confirm that MP2 severely overestimates binding energies of large complexes, producing relative errors of over 100% for several benchmark compounds. RPA relative errors consistently range between 5-10%, significantly less than reported previously using smaller basis sets, whereas spin-scaled MP2 methods show limitations similar to MP2, albeit less pronounced, and empirically dispersion-corrected DFAs perform almost as well as RPA. Regression analysis reveals a systematic increase of relative MP2 binding energy errors with the system size at a rate of approximately 1‰ per valence electron, whereas the RPA and dispersion-corrected DFA relative errors are virtually independent of the system size. These observations are corroborated by a comparison of computed rotational constants of organic molecules to gas-phase spectroscopy data contained in the ROT34 benchmark. To analyze these results, an asymptotic adiabatic connection symmetry-adapted perturbation theory (AC-SAPT) is developed which uses monomers at full coupling whose ground-state density is constrained to the ground-state density of the complex. Using the fluctuation–dissipation theorem, we obtain a nonperturbative “screened second-order” expression for the dispersion energy in terms of monomer quantities which is exact for non-overlapping subsystems and free of induction terms; a first-order RPA-like approximation to the Hartree, exchange, and correlation kernel recovers the macroscopic Lifshitz limit. The AC-SAPT expansion of the interaction energy is obtained from Taylor expansion of the coupling strength integrand. Explicit expressions for the convergence radius of the AC-SAPT series are derived within RPA and MBPT and numerically evaluated. Whereas the AC-SAPT expansion is always convergent for nondegenerate monomers when RPA is used, it is found to spuriously diverge for second-order MBPT, except for the smallest and least polarizable monomers. The divergence of the AC-SAPT series within MBPT is numerically confirmed within RPA; prior numerical results on the convergence of the SAPT expansion for MBPT methods are revisited and support this conclusion once sufficiently high orders are included. The cause of the failure of MBPT methods for NIs of large systems is missing or incomplete “electrodynamic” screening of the Coulomb interaction due to induced particle–hole pairs between electrons in different monomers, leaving the effective interaction too strong for AC-SAPT to converge. Hence, MBPT cannot be considered reliable for quantitative predictions of NIs, even in moderately polarizable molecules with a few tens of atoms. The failure to accurately account for electrodynamic polarization makes MBPT qualitatively unsuitable for applications such as NIs of nanostructures, macromolecules, and soft materials; more robust non-perturbative approaches such as RPA or coupled cluster methods should be used instead whenever possible.<br>

scholarly journals Sign-Problem-Free Fermionic Quantum Monte Carlo: Developments and Applications

2019 ◽  
Vol 10 (1) ◽  
pp. 337-356 ◽  
Author(s):  
Zi-Xiang Li ◽  
Hong Yao
Keyword(s):  
Monte Carlo ◽  
Quantum Monte Carlo ◽  
Hot Spot ◽  
High Temperature Superconductors ◽  
System Size ◽  
Many Body ◽  
Broken Symmetries ◽  
Sign Problem ◽  
Universal Quantum ◽  
Many Body Systems

Reliable simulations of correlated quantum systems, including high-temperature superconductors and frustrated magnets, are increasingly desired nowadays to further our understanding of essential features in such systems. Quantum Monte Carlo (QMC) is a unique numerically exact and intrinsically unbiased method to simulate interacting quantum many-body systems. More importantly, when QMC simulations are free from the notorious fermion sign problem, they can reliably simulate interacting quantum models with large system size and low temperature to reveal low-energy physics such as spontaneously broken symmetries and universal quantum critical behaviors. Here, we concisely review recent progress made in developing new sign-problem-free QMC algorithms, including those employing Majorana representation and those utilizing hot-spot physics. We also discuss applications of these novel sign-problem-free QMC algorithms in simulations of various interesting quantum many-body models. Finally, we discuss possible future directions of designing sign-problem-free QMC methods.

GLOBAL MINIMA FOR PdN (N = 5–80) CLUSTERS DESCRIBED BY SUTTON–CHEN POTENTIAL

2007 ◽  
Vol 18 (08) ◽  
pp. 1351-1359 ◽  
Author(s):  
HAYDAR ARSLAN
Keyword(s):  
Monte Carlo ◽  
Energy Surface ◽  
Central Atom ◽  
Low Energy ◽  
Global Minima ◽  
Many Body ◽  
Pd Clusters ◽  
Body Potential ◽  
Basin Hopping ◽  
Theoretical Results

The structure and energetics of Pd N (N = 5–80) clusters have been studied extensively by a Monte Carlo method based on Sutton–Chen many-body potential. The basin-hopping algorithm is used to find the low-energy minima on the potential energy surface for each nuclearity. A variety of structure types (icosahedral, decahedral and fcc closed-packed) are observed for Pd clusters. Some of the icosahedral global minima do not have a central atom. The resulting structures have been compared with the previous theoretical results.

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