Bayesian Networks (BNs) represent conditional probability relations among a set of random variables (nodes) in the form of a directed acyclic graph (DAG), and have found diverse applications in knowledge discovery. We study the problem of learning the sparse DAG structure of a BN from continuous observational data. The central problem can be modeled as a mixed-integer program with an objective function composed of a convex quadratic loss function and a regularization penalty subject to linear constraints. The optimal solution to this mathematical program is known to have desirable statistical properties under certain conditions. However, the state-of-the-art optimization solvers are not able to obtain provably optimal solutions to the existing mathematical formulations for medium-size problems within reasonable computational times. To address this difficulty, we tackle the problem from both computational and statistical perspectives. On the one hand, we propose a concrete early stopping criterion to terminate the branch-and-bound process in order to obtain a near-optimal solution to the mixed-integer program, and establish the consistency of this approximate solution. On the other hand, we improve the existing formulations by replacing the linear "big- " constraints that represent the relationship between the continuous and binary indicator variables with second-order conic constraints. Our numerical results demonstrate the effectiveness of the proposed approaches.
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ACS Phys Chem Au
November 2024
Condensed Matter Theory Group, Laboratory for Theoretical and Computational Physics, Center for Scientific Computing, Theory, and Data, Paul Scherrer Institute, 5232 Villigen, Switzerland.
Photoisomerization, the structural alteration of molecules upon absorption of light, is crucial for the function of biological chromophores such as retinal in opsins, proteins vital for vision and other light-sensitive processes. The intrinsic selectivity of this isomerization process (i.e.
View Article and Find Full Text PDFHeliyon
November 2024
Department of Environmental Science, Baylor University, Waco, TX 76798-7266, USA.
Phys Chem Chem Phys
December 2024
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India.
We report results of a theoretical study on photoinduced processes in 2-styrylpyridine. The geometries and the relative energies of the possible conformers were investigated using the second-order Møller-Plesset (MP2) and algebraic diagrammatic construction to second-order (ADC(2)) methods and the cc-pVTZ basis set. The complete active space self consistent field (CASSCF) method is used for locating the minimum-energy conical intersection (MECI) geometries between the S and S states.
View Article and Find Full Text PDFJ Phys Chem A
November 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
This work investigates Jahn-Teller conical intersections (CoIns) and the pseudo-Jahn-Teller effect on the formations and transformations of the low-lying singlet metal-ligand charge transfer (MLCT) excited states during the ultrafast evolution process of photoexcited [Ru(tpy)] (tpy = 2,2':6',2″-terpyridine). Longuet-Higgins' geometric phase analyses indicate that the potential energy surface (PES) crossing between charge transfer states MLCT and MLCT is a CoIn, originating from the change in diabatic Hamiltonian matrix elements around the CoIn. Moreover, an ⊗( + ) Jahn-Teller distortion can occur around the Franck-Condon and minimal energy CoIn (MECI) configurations, causing the molecule to distort spontaneously from the high-symmetry configuration to symmetry configurations that are close to it.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, PR China.
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