1. Simulation of X-ray Absorption Near Edge Spectroscopy (XANES) of Molecules Luke Campbell Shaul Mukamel Daniel Healion Rajan Pandey

2. Motivation X-ray Absorption Near Edge Spectroscopy (XANES) is an attractive tool for measuring local changes in electronic structure due to geometry and charge distribution of transient species. Recent advances in ultrashort (femtosecond to attosecond) x-ray pulses enable real time probing of optically induced electron motions and chemical processes. Time resolved XANES measures changes in geometry and charge distribution during and after the excitation. Theory can provide a guide for the design and interpretation of these measurements.

3. Basic Physics of X-ray Absorption X-ray absorption probes the unoccupied dipole allowed one electron density of states of a molecule in the vicinity of the absorbing atom.  µ(ω): absorption coefficient, intensity  σ(ω): absorption cross section.  : initial state with energy E i.  : final state with energy E f ; only transitions to unoccupied states are allowed.  : dipole operator (core size much smaller than x-ray wavelength). for depth x. Localized core → only local DOS contributes.

4.  Many-electron ground states (with and without core holes) are calculated using standard quantum chemistry codes. within density functional theory or Hartree-Fock approximation, (Z+1 approximation, where Z is the nuclear charge).  Electronically excited states are calculated using time dependent density functional theory (TDDFT) or time dependent Hartree-Fock (TDHF) theory. Sum Over States Method (SOS):  Computationally expensive, requires explicit calculation of excited states. Methodology

5. Transition Potential Method:  Uses a reference system with partially filled orbitals (incorporated in the StoBe Demon code).  Represents systems with different numbers of core holes by different occupation numbers of a single set of reference orbitals.  Computationally less expensive than SOS.  Works well for core level spectroscopies of small molecules.

6. Simulation of x-ray absorption near edge spectra (XANES) of molecules Start with the Deep Core Hamiltonian Neglect valence-core exchange ValenceCoreInteraction Electron-electron interaction One-electron valence terms Core hole potential → use Z+1 approximation, core hole approximated as point charge → equivalent to nuclear charge increased by 1.

7. Fermi’s Golden Rule gives the absorption cross section: Dipole operator in ν directionDipole matrix element → Initial wavefunction with energy E i. → Final wavefunction with energy E f. → Electron annihilation (creation) operator for orbital l.

8. Core-valence separation Deep core Hamiltonian → separate eigenvalue problem for valence and core electrons → can represent as product space In the Z+1 approximation: → Initial valence wavefunction. → Fully occupied core wavefunction. → Final valence wavefunction with core hole potential present. → Core wavefunction with orbital g unoccupied.

9. Effective valence Hamiltonians Core filled (initial state) valence Hamiltonian: Valence Hamiltonian with core hole in orbital g: The absorption spectrum:

10.  Basis set: Selection based on kind of chemical species in a molecule  Level of theory: Becke 3-parameter density functional with Lee-Yang-Parr correlation, Hartree-Fock approximation.  Code: GAUSSIAN-03  Geometry: from x-ray crystallography data (complex molecules).  Ground state:  Core excited state: singlet spin 5-15 singlet and/or triplet excited states with TDDFT or TDHF Z+1 approximation doublet spin 50 or more excited states with TDDFT/TDHF First principles computation of ground and excited state XANES Of chemical species  Use quantum chemistry code (Gaussian 03) to find electronic structure of ground and excited states.  Find energies and intensities of transitions from a given initial ground or excited state to possible final excited states.

11. [Ru(bpy) 3 ] 2+ Experimental XANES 1 eV valence shift of main peak (B → B ' ) after photoexcitation to 3 MLCT state. Appearance of new peak A ' after photoexcitation. L3-Edge

12. [Ru(bpy) 3 ] 2+ SOS Simulated XANES Ground state XANES (solid line) shows peak B. MLCT XANES (dottes) shows peak B' blue shifted by 1 eV and appearance of peak A'. Luke Campbell and Shaul Mukamel, J. Chem. Phys. 121, 12323 (2004). B3LYP/3-21G L3-Edge

13. Excited State Effects on X-ray Absorption Charge transfer to or from the absorbing atom can alter the energies and intensities of transitions to the bound states. Removing an electron makes the atom more positively charged, so more energy is needed to excite the core electron to orbitals farther from atom. Absorption peaks shift position When electrons are taken out of previously filled orbitals, new core → valence transitions are possible. When electrons are put into previously empty orbitals, peaks can disappear. Examples:

14. Single and Double Excitations Neglecting changes in orbitals due to core excitation: From any initial optically excited state, the final XANES state (a) can be reproduced with two excitations from the lowest core excited state (b). From some initial states, such as the ground state or HOMO to LUMO excitations, the final XANES state can be represented by one excitation from the lowest core excited state (b). Transition (1) gives ground state XANES (a), transition (2) gives HOMO to LUMO excitation XANES (c). l l l (a) (b) (c) (1) (2)

15. O H H X-ray photon 1.90 eV O HH Absorption Energy Water monomer Ionization potential 4a 1 2b 2 XANES XANES spectra of water (O K-edge) HF/6-311++G**

16. Sum Over States SOS (solid line) gives a good agreement with the experiment. Plots and numbers reproduced (except solid curve - SOS) from Ref: M. Cavalleri et al. J. Chem. Phys. Vol. 121, 10074 (2004) Peak splitting between the lowest transitions corresponding to 1a 1 → 4a 1 and 1a 1 → 2b 2 1.83 eV 2.04 eV 1.92 eV 1.90 eV

17. Methyl Alcohol SOS Transition Potential O K-Edge

18. XANES of Benzonitrile (N K-edge) TDDFT (B3LYP)/D95** TDHF/D95** Method/Basis Gives good agreement for the intensity ratio. However, peak splitting is not exact. Gives good agreement in the peak splitting. However, the intensity ratio is different than experiment. Ref: S. Carniato et al. Phys. Rev A 58, 022511 (2005).

19. X-Ray Fluorescence Hamiltonians in the Z+1 approximation:

20. Fluorescence Spectrum of Water Molecule Method/Basis SOS (HF)/D95V+* HF/Sadlej using Dalton program Ref: J.-H. Guo et al. Phys. Rev. Lett., Vol 89, 137402 (2002). 1b 1 3a 1 1b 2 Excitation at O K-edge

21. Methyl Alcohol HF/Sadlej

22. Fluorescence Spectra of Methyl Alcohol

23. Theoretical Challenges of Femtosecond X-Ray Simulations  Fast codes for excited state dynamics.  Codes for computing current profiles within molecules.  Study of X-ray fluorescence and four wave mixing when the molecule is initially in the optically excited state. Time Resolved Geometry Changes photodissociation changes in conformation vibrations  Immediately after electronic excitation, the molecule will begin to relax to a new equilibrium structure. This can involve:  Simulate quantum molecular dynamics to find forces on atoms in excited state.  Use mixed quantum/classical molecular dynamics for solvent.