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Extended Dynamically Weighted CASPT2: The Best of Two Worlds.

ABSTRACT: We introduce a new variant of the complete active space second-order perturbation theory (CASPT2) method that performs similarly to multistate CASPT2 (MS-CASPT2) in regions of the potential energy surface where the electronic states are energetically well separated and is akin to extended MS-CASPT2 (XMS-CASPT2) in case the underlying zeroth-order references are near-degenerate. Our approach follows a recipe analogous to that of XMS-CASPT2 to ensure approximate invariance under unitary transformations of the model states and a dynamic weighting scheme to smoothly interpolate the Fock operator between state-specific and state-average regimes. The resulting extended dynamically weighted CASPT2 (XDW-CASPT2) methodology possesses the most desirable features of both MS-CASPT2 and XMS-CASPT2, that is, the ability to provide accurate transition energies and correctly describe avoided crossings and conical intersections. The reliability of XDW-CASPT2 is assessed on a number of molecular systems. First, we consider the dissociation of lithium fluoride, highlighting the distinctive characteristics of the new approach. Second, the invariance of the theory is investigated by studying the conical intersection of the distorted allene molecule. Finally, the relative accuracy in the calculation of vertical excitation energies is benchmarked on a set of 26 organic compounds. We found that XDW-CASPT2, albeit being only approximately invariant, produces smooth potential energy surfaces around conical intersections and avoided crossings, performing equally well to the strictly invariant XMS-CASPT2 method. The accuracy of vertical transition energies is almost identical to MS-CASPT2, with a mean absolute deviation of 0.01-0.02 eV, in contrast to 0.12 eV for XMS-CASPT2.

SUBMITTER: Battaglia S

PROVIDER: S-EPMC7307887 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Extended Dynamically Weighted CASPT2: The Best of Two Worlds.

Battaglia Stefano S Lindh Roland R

Journal of chemical theory and computation 20200221 3

We introduce a new variant of the complete active space second-order perturbation theory (CASPT2) method that performs similarly to multistate CASPT2 (MS-CASPT2) in regions of the potential energy surface where the electronic states are energetically well separated and is akin to extended MS-CASPT2 (XMS-CASPT2) in case the underlying zeroth-order references are near-degenerate. Our approach follows a recipe analogous to that of XMS-CASPT2 to ensure approximate invariance under unitary transforma ...[more]

PMID: 32027802

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Project description:PurposeTo allow for comprehensive noninvasive diagnostics of coronary artery disease (CAD) by using three-dimensional (3D) image fusion of CT coronary angiography, CT-derived fractional flow reserve (CT FFR), whole-heart dynamic 3D cardiac MRI perfusion, and 3D cardiac MRI late gadolinium enhancement (LGE).Materials and methodsSeventeen patients (54 years ± 10 [standard deviation], one female) who underwent cardiac CT and cardiac MRI were included (combined subcohort of three prospective trials). Software facilitating multimodal 3D image fusion was developed. Postprocessing of CT data included segmentation of the coronary tree and heart contours, calculation of CT FFR values, and color coding of the coronary tree according to CT FFR. Postprocessing of cardiac MRI data included segmentation of the left ventricle (LV) in cardiac MRI perfusion and cardiac MRI LGE, co-registration of cardiac MRI to CT data, and projection of cardiac MRI perfusion and LGE values onto the high spatial resolution LV from CT.ResultsImage quality was rated as good to excellent (scores: 2.5-2.6; 3 = excellent). CT coronary angiography revealed significant stenoses in seven of 17 cases (41%). CT FFR was possible in 16 of 17 cases (94%) and showed pathologic flow in seven of 17 cases (41%), six of which coincided with cases revealing significant stenoses at CT coronary angiography. Cardiac MRI perfusion identified eight of 17 patients (47%) with hypoperfusion (ischemic burden of 17% ± 5). Cardiac MRI LGE showed myocardial scar in three of 17 cases (18%, scar burden of 7% ± 4). Conventional two-dimensional readout of CT coronary angiography and cardiac MRI resulted in eight of 17 cases (47%) with uncertain findings. Most of these divergent findings could be solved when adding information from CT FFR and 3D image fusion (six of eight, 75%).ConclusionMultimodal 3D cardiac image fusion is feasible and may help with comprehensive noninvasive CAD diagnostics.Supplemental material is available for this article.© RSNA, 2020.

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Extended Dynamically Weighted CASPT2: The Best of Two Worlds.

Publications

Extended Dynamically Weighted CASPT2: The Best of Two Worlds.

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