Comparison of an improved self-consistent lower bound theory with Lehmann’s method for low-lying eigenvalues

Ritz eigenvalues only provide upper bounds for the energy levels, while obtaining lower bounds requires at least the calculation of the variances associated with these eigenvalues. The well-known Weinstein and Temple lower bounds based on the eigenvalues and variances converge very slowly and their quality is considerably worse than that of the Ritz upper bounds. Lehmann presented a method that in principle optimizes Temple’s lower bounds with significantly improved results. We have recently formulated a Self-Consistent Lower Bound Theory (SCLBT), which improves upon Temple’s results. In this paper, we further improve the SCLBT and compare its quality with Lehmann’s theory. The Lánczos algorithm for constructing the Hamiltonian matrix simplifies Lehmann’s theory and is essential for the SCLBT method. Using two lattice Hamiltonians, we compared the improved SCLBT (iSCLBT) with its previous implementation as well as with Lehmann’s lower bound theory. The novel iSCLBT exhibits a significant improvement over the previous version. Both Lehmann’s theory and the SCLBT variants provide significantly better lower bounds than those obtained from Weinstein’s and Temple’s methods. Compared to each other, the Lehmann and iSCLBT theories exhibit similar performance in terms of the quality and convergence of the lower bounds. By increasing the number of states included in the calculations, the lower bounds are tighter and their quality becomes comparable with that of the Ritz upper bounds. Both methods are suitable for providing lower bounds for low-lying excited states as well. Compared to Lehmann’s theory, one of the advantages of the iSCLBT method is that it does not necessarily require the Weinstein lower bound for its initial input, but Ritz eigenvalue estimates can also be used. Especially owing to this property the iSCLBT method sometimes exhibits improved convergence compared to that of Lehmann’s lower bounds

Multi-State Density Functional Theory for Ground and Excited States

We report a rigorous formulation of multi-state density functional theory (MSDFT) that extends the Kohn-Sham (KS) energy functional for the ground state to a Hamiltonian matrix functional H[D] of the density matrix D in the space spanned by the lowest N adiabatic states. We establish a variational principle of MSDFT, which guarantees that the variational optimization results in a Hamiltonian matrix, whose eigenvalues are the lowest N eigen-energies of the system. We present an explicit expression of H[D] and introduce the correlation matrix functional. Akin to KS-DFT for the ground state, a universal multi-state correlation potential is derived for a two-state system as an illustrative example. This work shows that MSDFT is an exact density functional theory that treats the ground and excited states on an equal footing and provides a framework for practical applications and future developments of approximate functionals for excited states.

Computing Effective Hamiltonians of Coupled Electromagnetic Systems

In this paper, we present an efficient procedure to compute the effective Hamiltonian matrix of a coupled electromagnetic system consisting of subsystems that are coupled to a discrete number of channels through couplers. Each subsystem is described by its own effective non-Hermitian Hamiltonian and the corresponding Quasi-normal Modes (QNMs), while the coupler connecting the subsystems and the channels is described by the scattering matrix, which is equivalent to the transfer matrix, in terms of port vectors defined for the coupler. Due to the constraints imposed by the QNMs of the subsystems and the wave dynamics of the channels, as well as boundary condition constraints, constraint-free port vectors need to be chosen efficiently and they follow two rules: 1) port vectors forming loops with couplers; 2) port vectors of couplers with most constraints or with less freedom. With the constraint-free port vectors chosen, the effective Hamiltonian matrix of the coupled electromagnetic system can be obtained by imposing the boundary condition constraints. After the effective Hamiltonian is obtained, the eigenvalues, eigenvectors and dispersion relation of the coupled electromagnetic system, as well as other quantities such as the reflection and transmission, can be calculated. A 2D interstitial square coupled MRRs array is used as an example to demonstrate the computational procedure. The computation of the effective Hamiltonian matrix of a coupled electromagnetic system has many potential applications such as MRRs array, coupled Parity-Time Non-Hermitian electromagnetic system, as well as the dispersion relation of finite and infinite arrays.

Computing Effective Hamiltonians of Coupled Electromagnetic Systems

In this paper, we present an efficient procedure to compute the effective Hamiltonian matrix of a coupled electromagnetic system consisting of subsystems that are coupled to a discrete number of channels through couplers. Each subsystem is described by its own effective non-Hermitian Hamiltonian and the corresponding Quasi-normal Modes (QNMs), while the coupler connecting the subsystems and the channels is described by the scattering matrix, which is equivalent to the transfer matrix, in terms of port vectors defined for the coupler. Due to the constraints imposed by the QNMs of the subsystems and the wave dynamics of the channels, as well as boundary condition constraints, constraint-free port vectors need to be chosen efficiently and they follow two rules: 1) port vectors forming loops with couplers; 2) port vectors of couplers with most constraints or with less freedom. With the constraint-free port vectors chosen, the effective Hamiltonian matrix of the coupled electromagnetic system can be obtained by imposing the boundary condition constraints. After the effective Hamiltonian is obtained, the eigenvalues, eigenvectors and dispersion relation of the coupled electromagnetic system, as well as other quantities such as the reflection and transmission, can be calculated. A 2D interstitial square coupled MRRs array is used as an example to demonstrate the computational procedure. The computation of the effective Hamiltonian matrix of a coupled electromagnetic system has many potential applications such as MRRs array, coupled Parity-Time Non-Hermitian electromagnetic system, as well as the dispersion relation of finite and infinite arrays.

A Novel Graphene Modelling: Bottom up Approach - Band Gap Studies to Transport in Python

In this work we develop a computational, quantum level monolayer graphene nanoribbon (GNR) MOSFET of channel length of 10 and 20 nm, with a width of 2 nm and contacts of 2nm width is attached. To develop the MOSFET channel, a bottom up approach is adopted by developing the material model. First the material models of graphene nanoribbon is developed using pybinding module tool in python. The material models of monolayer, bilayer graphene nanoribbon are built on the principles of tight binding module. The methodology developed is based on the Hamiltonian matrix formulation that has been used to determine the E-k plots and LDOS plots of graphene monolayer, bilayer graphene nano ribbon. The GNR MOSFET that is structurally built in python is used to simulate graphene as a switch. Its band gap characteristics is presented as its performance as a switch and is verified with relevant work. Then GNR MOSFET is modelled using quantum principles of NEGF and greens function to determine the transmission characteristics and the I-V characteristics for channel lengths of 10 nm and 20 nm.

Charmonium Properties Using the Discrete Variable Representation (DVR) Method

The Schrödinger equation is solved numerically for charmonium using the discrete variable representation (DVR) method. The Hamiltonian matrix is constructed and diagonalized to obtain the eigenvalues and eigenfunctions. Using these eigenvalues and eigenfunctions, spectra and various decay widths are calculated. The obtained results are in good agreement with other numerical methods and with experiments.

Diabatic potential energy curves for the $$^4{\Pi} $$ states of SH

We present a diabatic representation of the potential energy curves (PECs) for the $$^4{{\Pi}} $$ 4 Π states of $$\mathrm {SH}$$ SH . Multireference, configuration interaction (MRCI) calculations were used to determine high-accuracy adiabatic PECs of both $$\mathrm {SH}$$ SH and $${\mathrm {SH}}^+$$ SH + from which the diabatic representation is constructed for $$\mathrm {SH}$$ SH . The adiabatic PECs exhibit many avoided crossings due to strong Rydberg-valence mixing. We employ the block diagonalization method, an orthonormal rotation of the adiabatic Hamiltonian, to disentangle the valence autoionizing and Rydberg $$^4\Pi $$ 4 Π states of $$\mathrm {SH}$$ SH by constructing a diabatic Hamiltonian. The diagonal elements of the diabatic Hamiltonian matrix at each nuclear geometry render the diabatic PECs and the off-diagonal elements are related to the state-to-state coupling. Care is taken to assure smooth variation and consistency of chemically significant molecular orbitals across the entire geometry domain.

Comparison of an Improved Self-consistent Lower Bound Theory with Lehmann’s Method for Low-lying Eigenvalues

Ritz eigenvalues only provide upper bounds for the energy levels, while obtaining lower bounds requires at least the calculation of the variances associated with these eigenvalues. The well-known Weinstein and Temple lower bounds based on the eigenvalues and variances converge very slowly and their quality is considerably worse than that of the Ritz upper bounds. Lehmann presented a method that in principle optimizes Temple’s lower bounds with significantly improved results. We have recently formulated a Self-Consistent Lower Bound Theory (SCLBT), which improves upon Temple’s results. In this paper we further improve the SCLBT and compare its quality with Lehmann’s theory. The Lánczos algorithm for constructing the Hamiltonian matrix simplifies Lehmann’s theory and is essential for the SCLBT. Using two lattice Hamiltonians, we compared the improved SCLBT with its previous implementation as well as with Lehmann’s lower bound theory. The novel SCLBT exhibits a significant improvement over the previous version. Both Lehmann’s theory and the SCLBT provide significantly better lower bounds than those obtained from Weinstein’s and Temple’s methods. Compared to each other, the Lehmann and SCLBT theories exhibit similar performance in terms of the quality and convergence of the lower bounds. By increasing the number of states included in the calculations, the lower bounds are tighter and their quality becomes comparable with that of the Ritz upper bounds. Both methods are suitable for providing lower bounds for low-lying excited states as well. Compared to Lehmann’s theory, one of the advantages of the SCLBT method is that it does not necessarily require the Weinstein lower bound for its initial input, but Ritz eigenvalue estimates can also be used. Especially owing to this property the SCLBT method sometimes exhibits improved convergence compared to that of Lehmann’s lower bounds.

Modeling Magnetic Interactions in High-Valent Trinuclear [Mn(IV)3O4]^4+ Complexes Through Highly Compressed Multi-Configurational Wave Functions

<p>In this work we apply a quantum chemical framework, recently designed in our laboratories, to rationalize the low-energy electronic spectrum and the magnetic properties of an homo-valent trinuclear [Mn^(IV)₃ O₄]⁴⁺ model of the oxygen-evolving center in photosystem II. The method is based on chemically motivated molecular orbital unitary transformations, and the optimization of spin-adapted many-body wave functions, both for ground- and excited-states, in the transformed MO basis. In this basis, the configuration interaction Hamiltonian matrix of exchange-coupled multi-center clusters is extremely sparse and characterized by a unique block diagonal structure. This property leads to highly compressed wave functions (oligo- or single-reference) and crucially enables state-specific optimizations. The reduced multi-reference character of the wave function greatly simplifies the interpretation of the ground- and excited-state electronic structures, and provides a route for the direct rationalization of magnetic interactions in these compounds, often considered a challenge in polynuclear transition-metal chemistry.</p>