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Journal of Physics Condensed Matter

Harnessing molecular excited states with Lanczos chains

Stefano Baroni A, Ralph Gebauer, Osman Barış Malcıoğlu, Yousef Saad, Paolo Umari, Jiawei Xian

Published Feb 3, 2010• 20 citations
Publisher

Abstract

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

DOI
10.1088/0953-8984/22/7/074204

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The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.
We present the generalization of the recursion method of Haydock and co-workers to systems of many interacting particles. This new method has close similarities to the memory function or Mori formalism, but with some important differences. Heisenberg's equation for the time evolution of a microscopic operator is recursively transformed into a tridiagonal matrix equation. This equation resolves the operator into components corresponding to transitions of different energies. The projected spectrum of transitions has a continued fraction expansion given by the elements of the tridiagonal matrix. We show that for an appropriate choice of inner product this density of transitions obeys a generalization of the black body theorem of electromagnetism, in that it is exponentially insensitive to distant parts of the system. This implies that the projected density of transitions is computationally stable and can be calculated even in macroscopic many-body systems. We argue that the physical content of the density of transitions is determined by the nature of its singular points, such as discrete transitions, continuous spectrum, band edges and van Hove singularities.
Previous work extending the Kohn–Sham theory to excited states was based on replacing the study of the ground-state energy as a functional of the ground-state density by a study of an ensemble average of the Hamiltonian as a functional of the corresponding average density. We suggest and develop an alternative to this description of excited states that utilizes the matrix of the density operator taken between any two states of the included space. Such an approach provides more detailed information about the states included, for example transition probabilities between discrete states of local one-body operators. The new theory is also based on a variational principle for the trace of the Hamiltonian over the space of states that we wish to describe, viewed, however, as a functional of the associated array of matrix elements of the density. This finds expression in a matrix version of the Kohn–Sham theory. To illustrate the formalism, we study a suitably defined weak-coupling limit, which is our equivalent of the linear response approximation. On this basis, we derive an eigenvalue equation that has the same form as an equation derived directly from the time-dependent Kohn–Sham equation and applied recently with considerable success to molecular excitations. We provide an independent proof, within the defined approximations, that the eigenvalues can be interpreted as true excitation energies.
We evaluate the density matrix of an arbitrary quantum mechanical system in terms of the quantities pertinent to the solution of the time-dependent density functional theory (TDDFT) problem. Our theory utilizes the adiabatic connection perturbation method of G\"orling and Levy, from which the expansion of the many-body density matrix in powers of the coupling constant $\ensuremath{\lambda}$ naturally arises. We then find the reduced density matrix ${\ensuremath{\rho}}_{\ensuremath{\lambda}}(\mathbf{r},{\mathbf{r}}^{\ensuremath{'}},t)$, which, by construction, has the $\ensuremath{\lambda}$ independent diagonal elements ${\ensuremath{\rho}}_{\ensuremath{\lambda}}(\mathbf{r},\mathbf{r},t)=n(\mathbf{r},t)$, n(r,t)n(\mathbf{r},t)n(r,t) being the particle density. The off-diagonal elements of ${\ensuremath{\rho}}_{\ensuremath{\lambda}}(\mathbf{r},{\mathbf{r}}^{\ensuremath{'}},t)$ contribute importantly to the processes unaccessible via the density, directly or by the use of the known TDDFT functionals. Of those, we consider the momentum-resolved photoemission, doing this to the first order in $\ensuremath{\lambda}$, i.e., on the level of the exact exchange theory. In illustrative calculations of photoemission from the quasi-2D electron gas and isolated atoms, we find quantitatively strong and conceptually far-reaching differences with the independent-particle Fermi's golden rule formula.
The matrix element of a general many-body operator between two Slater determinants is calculated explicitly. For this, a split-and-pair method is introduced that provides a convenient expression of Wick's theorem and simplifies many-body calculations. The same method is used to determine the generating function of the matrix elements of many-body operators. The split-and-pair method allows also for the diagonalization of the density correlation operators $:n({x}_{1})\ensuremath{\cdots}n({x}_{k}):$, where $n(x)={\ensuremath{\psi}}^{\ifmmode\dagger\else\textdagger\fi{}}(x)\ensuremath{\psi}(x)$ is the density operator. The relation between the split-and-pair method and quantum group theory is clarified.
We consider three distinct methods of calculating the vibronic levels and absorption spectra of molecular dimers coupled by dipole-dipole interactions. The first method is direct diagonalization of the vibronic Hamiltonian in a basis of monomer eigenstates. The second method is to use creation and annihilation operators leading in harmonic approximation to the Jaynes-Cummings Hamiltonian. The adiabatic approximation to this problem provides insight into spectral behavior in the weak and strong coupling limits. The third method, which serves as a check on the accuracy of the previous methods, is a numerically exact solution of the time-dependent Schrodinger equation. Using these methods, dimer spectra are calculated for three separate dye molecules and show good agreement with measured spectra.