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Anion Electronic Structure and Correlated, One-electron Theory. J. V. Ortiz Department of Chemistry and Biochemistry Auburn University Workshop on Molecular Anions and Electron-Molecule Interactions in Honor of Professor Kenneth Jordan July 1, 2007

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anion electronic structure and correlated one electron theory

Anion Electronic Structure and Correlated, One-electron Theory

J. V. Ortiz

Department of Chemistry and Biochemistry

Auburn University

Workshop on Molecular Anions and Electron-Molecule Interactions in Honor of

Professor Kenneth Jordan

July 1, 2007

Park City, Utah


National Science Foundation

Defense Threat Reduction Agency

  • Symposium Organizers
  • Jack Simons
  • Brad Hoffman
  • Auburn University
  • Department of Chemistry and Biochemistry
  • Auburn Coworkers
  • UNAM Collaborators:
  • Ana Martínez
  • Alfredo Guevara
quantum chemistry s missions
Deductive agenda:

Deduce properties of molecules from quantum mechanics

Calculate chemical data, especially if experiments are difficult or expensive

Inductive agenda:

Identify and explain patterns in structure, spectra, energetics, reactivity

Deepen and generalize the principles of chemical bonding

Quantum Chemistry’s Missions

G. N. Lewis

E. Schrödinger


Electron Propagator




Molecular Orbital



one electron equations
Hartree Fock Theory

Hartree Fock Equations:

(Tkin + Unucl + JCoul - Kexch)φiHF ≡

F φiHF=εiHF φiHF

Same potential for all i:

core, valence, occupied, virtual.

εiHF includes Coulomb and exchange contributions to IEs and EAs

Electron Propagator Theory

Dyson Equation:

[F + ∑(εiDyson)]φiDyson = εiDyson φiDyson

Self energy, ∑(E): Energy dependent, nonlocal potential that varies for each electron binding energy

εiDyson includes Coulomb, exchange, relaxation and correlation contributions to IEs and EAs

φiDyson describes effect of electron detachment or attachment on electronic structure

One-electron Equations
dyson orbitals feynman dyson amplitudes
Dyson Orbitals (Feynman-Dyson Amplitudes)
  • Electron Detachment (IEs)

φiDyson(x1) =



  • Electron Attachment (EAs)

φiDyson(x1) =

(N+1)-½∫ Ψi,N+1(x1,x2,x3,...,xN+1)Ψ*N(x2,x3,x4,…,xN+1) dx2dx3dx4…dxN+1

  • Pole strength

Pi = ∫|φiDyson(x)|2dx

0 ≤ Pi ≤ 1

electron propagator concepts
Electron Propagator Concepts

Electron Correlation

Dyson Orbital

Canonical MO

Correlated Electron

Binding Energy

Orbital Energy

Integer Occupation


Pole Strengths





accuracy versus interpretability
Accuracy versus Interpretability
  • Does electron propagator theory offer a solution to Mulliken’s dilemma?

The more accurate the

calculations become,

the more the concepts

vanish into thin air.

- R. S. Mulliken

dyson orbitals for u and t ies
Dyson Orbitals for U and T IEs








Methyl (CH3) participation

uracil versus thymine
Uracil versus Thymine
  • Methyl group destabilizes π orbitals with large amplitudes at nearest ring atom
  • Therefore, IE(T) < IE(U)
  • Valid principles for substituted DNA bases, porphyrins and other organic molecules
a self energy for large molecules p3
A Self-Energy for Large Molecules: P3
  • Neglect off-diagonal elements of Σ(E) in canonical MO basis: φiDyson(x) = Pi½φiHF-CMO(x)
  • Partial summation of third-order diagrams
  • Arithmetic bottleneck: oN4 (MP2 partial integral transformation)
  • Storage bottleneck: o2v2 in semidirect mode
  • Abelian, symmetry-adapted algorithm in G03
formulae for p3 e
Formulae for ΣP3(E)

ΣP3pq(E) =

½Σiab <pi||ab><ab||qi> Δ(E)-1iab +

½Σaij <pa||ij>(<ij||qa> + Wijqa) Δ(E)-1aij +

½Σaij Upaij(E)<ij||qa>Δ(E)-1aij


Δ(E)-1pqr = (E + εp – εq – εr)-1

Wijqa = ½Σbc<bc||qa><ij||bc> Δ-1ijbc

+ (1-Pij)Σbk<bi||qk><jk||ba> Δ-1jkab

Upaij(E) = - ½Σkl<pa||kl><kl||ij> Δ(E)-1akl

- (1 – Pij) Σbk<pb||jk><ak||bi> Δ(E)-1bjk

p3 performance
P3 Performance
  • 31 Valence IEs of Closed-Shell Molecules:


MAD (eV) = 0.20 (tz)

  • 10 VEDEs of Closed-Shell Anions:


MAD (eV) = 0.25 (a-tz)

  • Arithmetic bottleneck: o2v3 for Wijqa
  • Storage bottleneck: <ia||bc> for Wijqa
invitation to propagate
Invitation to Propagate

Input to Gaussian 03

# OVGF 6-311G** iop(9/11=10000)

P3 Electron Propagator for Water

0 1


H 1 0.98

H 1 0.98 2 105.

Available diagonal approximations for Σ(E):

Second order, Third order, P3, OVGF (versions A, B & C)

nucleotides gaseous spectra
Nucleotides: Gaseous Spectra
  • Nucleotides: phosphate-sugar-base DNA fragments
  • Electrospray ion sources
  • Magnetic bottle detection
  • High resolution laser spectroscopy of ions, mass spectrometry
  • Goal: predict photoelectron spectra of anionic nucleotides (vertical electron detachment energies or VEDEs)
photoelectron spectra of 2 deoxybase 5 monophosphate anions
Photoelectron Spectra of 2’-deoxybase 5’-monophosphate Anions


Anomalous peak for dGMP

Base = adenine


G: lowest IE

of DNA bases

Base = cytosine


Base = guanine

Dyson orbitals for

lowest VEDEs:

phosphate or base?


Base = thymine

L-S.Wang, 2004

damp isomers and energies
DAMP Isomers and Energies

0 kcal/mol



dgmp isomers and energies
DGMP Isomers and Energies

0 kcal/mol



hydrogen bonds dgmp vs damp
Hydrogen Bonds: DGMP vs DAMP
  • DGMP: G amino to Phosphate oxygen
  • DAMP: Sugar hydroxy to Phosphate oxygen
nucleotide electronic structure
Nucleotide Electronic Structure
  • Phosphate anion reduces Base VEDEs by several eV
  • Base also increases Phosphate VEDEs
  • Therefore, Base and Phosphate VEDEs

are close

  • Differential correlation effects are large
  • Koopmans ordering is not reliable
a simple renormalized self energy p3
A Simple, Renormalized Self-Energy: P3+

ΣP3+pq(E) =

½Σiab <pi||ab><ab||qi> Δ(E)-1iab +

[1+Y(E)]-1 ½Σaij<pa||ij>(<ij||qa> + Wijqa) Δ(E)-1aij + ½Σaij Upaij(E)<ij||qa>Δ(E)-1aij


Y(E) = {-½Σaij<pa||ij>Wijqa Δ(E)-1aij} {½Σaij<pa||ij><ij||qa> Δ(E)-1aij}-1

p3 performance1
P3+ Performance
  • 31 Valence IEs of Closed-Shell Molecules:


MAD (eV) = 0.19 (tz), 0.19 (qz)

  • 10 VEDEs of Closed-Shell Anions:


MAD (eV) = 0.11 (a-tz), 0.13 (a-qz)

reactivity of al 3 o 3 with h 2 o
Reactivity of Al3O3- with H2O
  • Wang: first anion photoisomerization
  • Jarrold: Al3O3-(H2O)n photoelectron spectra n=0,1,2
  • Distinct profile for n=1
  • Similar spectra for n=2 and n=0
cluster vedes and dyson orbitals
Cluster VEDEs and Dyson Orbitals




strong initial state correlation
Strong Initial State Correlation
  • Need better reference orbitals for:

diradicaloids, bond dissociation, unusual bonding …

  • Generate renormalized self-energy with approximate Brueckner reference determinant
a versatile self energy bd t1
A Versatile Self-Energy: BD-T1
  • Asymmetric Metric:



  • Galitskii-Migdal energy =

BD (Brueckner Doubles, Coupled-Cluster)

  • Operator manifold: f~a†aa=f3
  • Discard only 2ph-2hp couplings
applications of the bd t1 approximation
Applications of theBD-T1 Approximation
  • Vertical Electron Detachment Energies of Anions: MAD=0.03 eV
  • 1s Core Ionization Energies: MAD = 0.2%
  • Valence IEs of Closed-Shell Molecules:

MAD = 0.15 eV

  • IEs of Biradicaloids: MAD = 0.08 eV
bowen s photoelectron spectrum of nh 4
Bowen’s Photoelectron Spectrum of NH4-

B: Mysterious low-VEDE peak

Not due to hot NH4-

Variable relative intensity

Another isomer of NH4-?

A: H- detachment

with vibrational

excitation of NH3

X: H-(NH3)

NH3 increases H- VEDE





computational search nh 4 structures
Computational Search: NH4- Structures

Hydride anion: H-

H-(NH3) constituents:

Ammonia molecule: NH3

Lewis: 1 electron pair

H nucleus has 1+ charge

Negative charge attracts

+ end of polar NH bond

Lewis: 3 electron pairs

shared in polar NH bonds

+ 1 unshared pair on N

Partial + charge on H’s

Partial – charge on N



accounts for

dominant peaks

computational search what is the structure for the low vede peak
Computational Search:What is the structure for the low-VEDE peak?

Idea: NH2-(H2) anion-molecule complex

Reject: spectral peak would be high-VEDE, not low

Idea: NH4- has 5 valence e- pairs

Deploy in 4 N-H bonds and 1 unshared pair

at the 5 vertices of a trigonal biprism or

square pyramid

Calculations find no such structures!

Instead, they spontaneously rearrange ….

to a heretical structure
….to a heretical structure!

Tetrahedral NH4- has 4

equivalent N-H bonds

Defies Lewis theory

Defies valence shell

electron pair

repulsion theory

Structure similar to that of NH4+

So where are the 2 extra electrons?

structural confirmation experiment and theory
Structural Confirmation:Experiment and Theory

Predicted VEDEs from Electron Propagator Theory

for Anion(molecule) and Tetrahedral forms of NH4-

coincide with peaks from photoelectron spectrum

dyson orbitals for vedes of nh 4
Dyson Orbitals for VEDEs of NH4-

H-(NH3) has 2 electrons

in hydride-centered orbital

with minor N-H delocalization.

VEDE is 1.07 eV

Tetrahedral NH4- has 2

diffuse electrons located

chiefly outside of NH4+ core.

VEDE is 0.47 eV

irc t d nh 4 h nh 3
IRC: Td NH4- -> H-(NH3)

Energy (au)

Intrinsic Reaction Coordinate

double rydberg anions
Double Rydberg Anions
  • Highly correlated motion of two diffuse (Rydberg) electrons in the field of a positive ion (NH4+ , OH3+)
  • United atom limit is an alkali anion: Na-
  • Extravalence atomic contributions in Dyson orbitals



bowen s photoelectron spectrum of n 2 h 7
Bowen’s Photoelectron Spectrum of N2H7-

X: H-(NH3)2 e- detachment

B & C: two low EBEs!






calculated n 2 h 7 structures
Calculated N2H7- Structures
  • H-(NH3)2 anion-

molecule complex

  • NH4-(NH3) anion-

molecule complex

with tetrahedral NH4-

  • N2H7- with hydrogen bond (similar to N2H7+ )
n 2 h 7 vedes and dyson orbitals
N2H7- VEDEs and Dyson Orbitals

H-(NH3)2 has hydride centered Dyson orbital

EPT predicts 1.49 eV for VEDE

Peak observed in spectrum at 1.46 ± 0.02 eV

Dyson orbital concentrated near NH4-

EPT predicts 0.60 eV for VEDE

Peak observed at 0.58 ± 0.02 eV

Dyson orbital concentrated near 3 hydrogens

EPT predicts 0.42 eV for VEDE

Peak observed at 0.42 ± 0.02 eV

assignment of n 3 h 10 ebes to double rydberg anions
Assignment of N3H10-EBEs to Double Rydberg Anions
  • (NH4-)(NH3)2 : 0.66 (Expt.) 0.68 (EPT)
  • (N2H7-)(NH3) : 0.49 (Expt.) 0.49 (EPT)
  • (N3H10-) : 0.42 (Expt.) 0.40 (EPT)


o 2 h 5 and n 2 h 7 structures
O2H5- and N2H7- Structures




o 2 h 5 vedes and dyson orbitals
O2H5- VEDEs and Dyson Orbitals

H-(H2O)2 VEDE: 2.36 eV

H-bridged VEDE: 0.48 eV

Ion-dipole VEDE: 0.74 eV

electron pair concepts old and new
Electron Pair Concepts: Old and New

Chemical bonds arise

from pairs of electrons

shared betweenatoms

G.N. Lewis

I. Langmuir

W.N. Lipscomb

Unshared pairs

localized on single atoms

affect bond angles

Molecular cations may

bind an e- pair peripheral

to nuclear framework:

Double Rydberg Anions

R.J. Gillespie

R.S. Nyholm

electron propagator theory and quantum chemistry s missions
Electron Propagator Theory and Quantum Chemistry’s Missions
  • Deductive, quantitative theory:

Prediction and interpretation enable dialogue with experimentalists requiring accurate data

  • Inductive, qualitative theory:

Orbital formalism generalizes and deepens qualitative notions of electronic structure, relating structure, spectra and reactivity