Molecules in strong magnetic fields

Trygve Helgaker, Kai Lange, Alessandro Soncini, and Erik Tellgren

Centre for Theoretical and Computational Chemistry

Department of Chemistry, University of Oslo, Norway

14th European Symposium on Gas-Phase Electron Diffraction

M. V. Lomonosov Moscow State University
Moscow, June 24–28 2011

Trygve Helgaker, Kai Lange, Alessandro Soncini, and Erik Tellgren

Molecules
(CTCC,
in strong
University
magnetic
of Oslo)
fields 14th European Symposium on GED 1 / 22
Outline

1 Molecular magnetism

2 The LONDON program

3 Molecular diamagnetism and paramagnetism

4 The helium atom

5 The H2 and He2 molecules

6 Excitations in strong fields

7 Conclusions

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 2 / 22
Molecules in weak magnetic fields
I Molecular magnetism is usually studied perturbatively
X X
1
E (B) = E (0) − mα Bα − 2
χαβ Bα Bβ + · · ·
α αβ

I such an approach is highly successful and widely used in quantum chemistry

I molecular magnetic properties are accurately described by perturbation theory
I Example: 200 MHz NMR spectra of vinyllithium

experiment RHF

0 100 200 0 100 200

MCSCF B3LYP

0 100 200 0 100 200

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 3 / 22
Molecules in strong magnetic fields
I However, the field dependence of the energy can be complicated
I the energy of C20 (ring conformation) plotted against B (atomic units)

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-0.04 -0.02 0.02 0.04

I such behaviour cannot be described or understood perturbatively

I We have undertaken a nonperturbative study of molecular magnetism
I gives new insight into molecular electronic structure
I describes atoms and molecules observed in astrophysics (stellar atmospheres)
I provides a framework for studying the current dependence of the universal density functional
I enables evaluation of many properties by finite-difference techniques

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 4 / 22
The electronic Hamiltonian
I The non-relativistic electronic Hamiltonian (atomic units) in a magnetic field B is given by
X
H = T + VCoulomb + 12 BLz + Bsz + 1
8
(xi2 + yi2 )B 2
i
I T is the kinetic-energy operator and VCoulomb = Ven + Vee + Vnn the Coulomb operator
I L and s are the orbital and spin angular momentum operators
I one atomic unit of B corresponds to 2.2 × 105 T = 2.2 × 109 G
I Coulomb regime: B ≈ 0 a.u.
I earth-like conditions: Coulomb interactions dominate
I magnetic interactions are treated perturbatively
I earth magnetism 10−10 , loudspeaker 10−5 , NMR 10−4 ; pulsed laboratory field 10−3 a.u.
I Landau regime: B  1 a.u.
I astrophysical conditions: magnetic interactions dominate
I Coulomb interactions are treated perturbatively
I harmonic-oscillator Hamiltonian with force constant B 2 /4: Landau levels
I the electrons are confined in the transverse directions by the magnetic field
I neutron stars 103 –104 a.u.; magnetars 105 a.u.
I Intermediate regime: B ≈ 1 a.u.
I the Coulomb and magnetic interactions are equally important
I complicated behaviour resulting from interplay of linear and quadratic terms
I white dwarves: up to about 1 a.u.
I We here consider the weak and intermediate regimes (B ≤ 15 a.u.)

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 5 / 22
The LONDON program
I The electronic Hamiltonian in a magnetic field
X
H = T + VCoulomb + 12 B · L + B · s + 1
8
(B × ri ) · (B × ri )
i
contains the orbital-angular momentum operator
X
L = −i (ri − O) × ∇i (1)
i
I this operator is imaginary and depends on an arbitrary gauge origin O
I our results should be invariant to the choice of O
I Standard quantum-chemistry program cannot treat molecules in finite magnetic fields
I we must optimize a complex wave function
I we must use London atomic orbitals to ensure gauge-origin invariance
1 
ωlm (rK , B) = exp 2
iB × (O − K) · r χlm (rK )
I We have developed the LONDON code for this purpose
I complex wave functions with London atomic orbitals
I Hartree–Fock (RHF, UHF, GHF) and Kohn–Sham theories
I FCI and MCSCF theories
I first-order properties including molecular gradients for geometry optimizations
I linear response theory

I The code has been written by Erik Tellgren, Kai Lange, and Alessandro Soncini
I mostly C++, some Fortran 77
I modular but not highly optimized yet
I C
20 is a “large” system

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 6 / 22
Diamagnetism and paramagnetism
I When a magnetic field is applied to a molecule, one of two things can happen:
154114-8 Tellgren, Soncini, and Helgaker
I the energy is lowered: molecular paramagnetism
a) b) −3
I the energy is raised: molecular diamagnetism 14
x 10

0.1
12
I Open-shell molecules are paramagnetic
0.08 10
I the molecule reorients the permanent magnetic moment and lowers the energy
8
0.06

I Closed-shell molecules may be diamagnetic or paramagnetic 6

0.04
4
I the induced magnetic moment may oppose or enhance the external field
0.02
I most molecules are diamagnetic, opposing the external field by Lenz’ law 2

I in some systems, orbital unquenching results in paramagnetism 0 0

−0.1 −0.05 0 0.05 0.1 −0.1

I RHF calculations
154114-8 of the field-dependence for J.three
Tellgren, Soncini, and Helgaker closed-shell
Chem. Phys. 129, 154114 !2008" systems:
c) d)
a) b) −3
x 10
14 0

0.1 −0.002 0.02

12
−0.004
0.01
0.08 10 −0.006

−0.008
0
8
0.06 −0.01

6 −0.012 −0.01
0.04
−0.014
4 −0.02
−0.016
0.02
2 −0.018 −0.03

−0.02
0 0
−0.1 −0.05 0 0.05 0.1 −0.1 −0.05 0 0.05 0.1 −0.1 −0.05 0 0.05 0.1 0 0.0

FIG. 1. Energy as a function of the magnetic field for different systems. Triangles represent re
fitting polynomials. !a" Benzene !with the aug-cc-pVDZ basis" illustrates the typical case of diam
field. !b" Cyclobutadiene !aug-cc-pVDZ" deviates from the typical case by exhibiting a no
ac) benzene (aug-cc-pVDZ): typical
d) diamagnetic quadratic dependence on an out-of-plane field
monohydride !aug-cc-pVTZ" is an interesting case of positive magnetizability for a perpendic
hydride !aug-cc-pVTZ" in a larger range of perpendicular fields, exhibiting a clearly nonpertur
0
b cyclobutadiene (aug-cc-pVDZ): diamagnetic non-quadratic dependence on an out-of-plane field
−0.002 0.02
c BH (aug-cc-pVTZ): paramagnetic dependence on a perpendicular
−0.004
field are in fact positive and large enough to
linear magnetizability For the
make even the average magnetizability positive !paramag- hypermagne
0.01
−0.006 netic". It is therefore interesting to verify via our finite-field fitting proce
−0.008
London-orbital approach whether this very small system is data points
Helgaker et al. (CTCC, University of Oslo) Molecules
0 in strong magnetic fields 14th
indeed European
characterized by a Symposium
particularly large on GEDmag-
nonlinear 7gree
/ 22of the
 0.015 ! 0.003

0.01
Stabilizing field strength for paramagnetic molecules 0.005
! 0.004

B !au"
! 0.005

I However, plots over a larger range reveal

0.02 0.04 0.06 0.08
that 0.1 0.12

all closed-shell systems become diamagnetic in sufficiently strong fields:

c) d)
W!W0 !au" W!W0 !au" W!W0 !au"
B !au"
BH C8H8: total energy C12H12: total energy
a) 0.002
0.05 0.1 0.15 0.2 0.25 0.3
0.004 0.0015 STO!3G, Bc " 0.018
! 0.01 STO!3G, Bc " 0.24 STO!3G, Bc " 0.035
6!31G, Bc " 0.018
DZ, Bc " 0.22 6!31G, Bc " 0.034
0.001 cc!pVDZ, Bc " 0.016
aug!DZ, Bc " 0.23 cc!pVDZ, Bc " 0.032
0.002
! 0.02 0.0005

B !au"
! 0.03 0.01 0.02 0.03 0.04 0.05 0.06 0.005 0.01 0.015 0.02 0.025 0.03

! 0.0005

! 0.04 ! 0.002
! 0.001

W!W0 !au"
B !au"
CH#
b)
0.1 0.2 0.3 0.4 0.5 0.6
I The transition occurs at a characteristic stabilizing critical field strength Bc
! 0.02
I B ≈ 0.22 perpendicular to principal axis for BH
c STO3!G, Bc " 0.43
! 0.04 I B ≈ 0.032 along the principal axis for antiaromatic octatetraene C H
c DZ, Bc " 0.44 8 8
I B ≈ 0.016 along the principal axis for antiaromatic [12]-annulene C H
! 0.06
c aug!DZ, Bc " 0.45 12 12

I The stabilizing field strength decreases with increasing molecular size

! 0.08
I strongest laboratory fields attainable: 10−3 a.u.
! 0.1 I B is inversely proportional to the area of the molecule normal to the field
c
I we estimate that B should be observable for C H
! 0.12
c 72 72

W!W0 !au"
I We may in principle separate such molecules by applying a field gradient
B !au"
MnO4!
c)
0.1 0.2 0.3 0.4 0.5 0.6 0.7
! 0.1 STO!3G, Bc " 0.45
Helgaker et al. (CTCC, UniversityWachters,
of Oslo) Bc " 0.50 Molecules in strong magnetic fields 14th European Symposium on GED 8 / 22
Analytical model for the diamagnetic transition
I The diamagnetic transition arises from an interplay between linear and quadratic terms
I it can be understood from a simple two-level model
I Molecular orbitals relevant for BH:

1sB , 2σBH , 2px , 2py , 2pz (molecule along z axis)

I Ground and excited states:

|0i = |1sB2 2σBH

2
2pz2 |, |1x i = |1sB2 2σBH
2
2pz 2px |, |1y i = |1sB2 2σBH
2
2pz 2py |

I Let us apply a perpendicular magnetic field in the y direction:

HB = 21 BLy + 18 B 2 (x 2 + z 2 )
I This leads to the following Hamiltonian matrix where |1i = |1x i:

E0 − 21 χ0 B 2
   
h0|H|0i h0|H|1i iµB
H(B) = =
h1|H|0i h1|H|1i −iµB E1 − 12 χ1 B 2
where we have introduced
χ0 = − 14 h0|x 2 + z 2 |0i < 0, χ1 = − 41 h1|x 2 + z 2 |1i < 0, µ = − 21 ih0|Ly |1i
I Interpretation:
I the diabatic states |0i and |1x i are uncoupled at B = 0 and diamagnetic
I in a magnetic field, they become coupled by Ly
I the resulting adiabatic ground state may be either diamagnitic or paramagnetic

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 9 / 22
Energy levels of the two-level model
I The excited state assumed ∆E = 0.02 above the ground-state at B = 0
I magnetizabilities of the diabatic states: χ = −28 (red) and χ = −16 (yellow)
0 1
I Plots for different values of the coupling-matrix element µ:
I uncoupled (0), diamagnetic (0.2), nonmagnetic (0.374), and paramagnetic (0.6)

0.09 0.09

0.06 0.06

0.03 0.03

-0.1 0.1 -0.1 0.1

-0.03 -0.03

0.09 0.09

0.06 0.06

0.03 0.03

-0.1 0.1 -0.1 0.1

-0.03 -0.03

I the magnetizability of the adiabatic ground state:

χGS = χ0 + µ2 /∆E = −7, −5, 0, 11
I Paramagnetism results from avoided crossings at finite magnetic fields

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 10 / 22
Induced rotation of the electrons
I The magnetic field induces a rotation of the electrons about the field direction:
I the amount of rotation is the expectation value of the kinetic angular-momentum operator

h0|Λ|0i = 2E 0 (B) = −2M, Λ = r × π, π =p+A

I positive rotation increases the energy; negative rotation reduces the energy
I Diamagnetic closed-shell molecules:
I h0|Λ|0i aligns with the field according to Lenz’ law, increasing the energy 1
2 h0|Λ|0i ·B
I Paramagnetic closed-shell molecules:
I h0|Λ|0i first aligns against the field, decreasing the energy
Example 2: Non-perturbative phenomena
I h0|Λ|0i goes through a minimum (maximum rotation) at the inflection point E 00 (B) = 0
I h0|Λ|0i then increases again until rotation vanishes at B
c
I h0|Λ|0i finally aligns with the field, making the system diamagnetic
BH properties (aug-cc-pVDZ) as function of perpendicular field:
Energy Angular momentum Nuclear shielding integral
1
!25.11 Boron
0.4 Hydrogen
!25.12

Lx / |r ! Cnuc|
0.5 0.2
!25.13
Lx(Bx)
E(Bx)

!25.14 0
0
!25.15
!0.2
!25.16
!0.5
0 0.2 0.4 0 0.2 0.4 0 0.2 0.4

I Orbital energies HOMO!LUMO gap Singlet excitation energies

there is no net rotation at the stationary points B = 0 and B = Bc
0.5
0.1 0.4
0.48
Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 0.35
14th European Symposium on GED 11 / 22
C20 : more structure

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-0.04 -0.02 0.02 0.04

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 12 / 22
The helium atom
I The helium energy behaves in simple manner in magnetic fields (left)
I an initial quadratic diamagnetic behaviour is followed by a linear increase in B
I this is expected from the Landau levels (harmonic potential increases as B 2 )
I The orbital energies behave in a more complicated manner (middle)
I the initial behaviour is determined by the angular momentum
I beyond B ≈ 1, all energies increase with increasing field
I HOMO–LUMO gap increases, suggesting a decreasing importance of electron correlation
I The atom becomes squeezed in the magnetic field (right)
I this is particularly true for the transverse directions
I the cyclotron radius is proportional to B −1/2
I special basis sets are need for strong fields (Landau orbitals)
Helium atom, RHF/augïccïpVTZ Helium atom, RHF/augïccïpVTZ
Helium atom, RHF/augïccïpVTZ
3 10 0.8

0.7
2 8

Qxx
0.6

Quadrupole moment [bohr2]

Qyy
1 6
Qzz
Energy, E [Hartree]

Orbital energy, ¡ [Hartree]

0.5
0 4

0.4

ï1 2

0.3

ï2 0
0.2

ï3 ï2
0 1 2 3 4 5 6 7 8 9 10
0.1
0 1 2 3 4 5 6 7 8 9 Field, B [au] 0 1 2 3 4 5 6 7 8 9
Field, B [au] Field, B [au]

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 13 / 22
The helium natural occupation numbers
I The natural occupation numbers are eigenvalues of the one-electron density matrix
I The FCI occupation numbers approach 2 and 0 strong fields
I decreasing importance of dynamical correlation in magnetic fields
I the two electrons rotate in the same direction about the field direction

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 14 / 22
The H2 molecule
I Magnetic fields strongly affect chemical bonding and potetial energy surfaces

I Potential energy curves of H2 in a parallel field B = 0, 5, 10 a.u.

I FCI/aug-cc-pVDZ calculations with energy set to zero at full dissociation

H2 /aug-cc-pVDZ, lowest singlet, field parallel to bond H2 /aug-cc-pVDZ, lowest triplet, field parallel to bond
0.5
0.0

0.0
0.5

1.0 0.5
E (Ha)

E (Ha)
1.5 1.0

2.0
1.5
B = 0.0 a.u. B = 0.0 a.u.
2.5 B = 5.0 a.u. B = 5.0 a.u.
B = 10.0 a.u. 2.0
B = 10.0 a.u.
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
R (bohr) R (bohr)

I H2 becomes strongly bound in strong fields

I the basis set is too small to give quantitative results
I The low-spin triplet component (ββ) becomes the ground state at about 0.25 a.u.
I the Zeeman interaction contributes BMs to the energy

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 15 / 22
Electron rotation and correlation in H2
I The energy of H2 in the singlet state increases in a parallel field (left)
I the field induces a rotation of the electrons h0|Λz |0i about the molecular axis (right)

I The occupation numbers indicate reduced importance of dynamical correlation

I the two electrons rotate in the same direction, reducing the chance of near encounters

H2 /cc-pVTZ, optimized geometry, field parallel to bond

2.00

1.98
Cummulative occupation number

1.96

1.94

1.92

1.90 0 1 2 3 4
B (a.u.)

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 16 / 22
The covalently bound He2 molecule
I We have also performed FCI/aug-cc-pVDZ calculations on the helium dimer
I energy set to zero for full dissociation in all cases
I We have considered the lowest singlet, triplet and quintet states
I in the absence of a field, only the triplet state is covalently bound
I in the presence of a field, all states become strongly bound

He2 /aug-cc-pVDZ, lowest singlet, field parallel to bond He2 /aug-cc-pVDZ, lowest triplet, field parallel to bond He2 /aug-cc-pVDZ, lowest quintet, field parallel to bond
0.3
0.0
0.2
0.0
0.2 0.1

0.0
E (Ha)

E (Ha)

E (Ha)
0.5 0.4
0.1

0.2
0.6
1.0 B = 0.0 a.u. B = 0.0 a.u. 0.3 B = 0.0 a.u.
B = 5.0 a.u. B = 5.0 a.u. B = 5.0 a.u.
B = 10.0 a.u. 0.8 B = 10.0 a.u. 0.4 B = 10.0 a.u.
B = 15.0 a.u. B = 15.0 a.u. B = 15.0 a.u.
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 0.5 1 2 3 4 5 6 7 8
R (bohr) R (bohr) R (bohr)

I In magnetic fields, spin multiplets are split

I within each multiplet, the low-spin component has lowest energy
I Increasing magnetic fields favor low-spin components of high-spin states
I in weak fields, the ground state is a singlet
I in strong fields, the ground state is the low-spin quintet

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 17 / 22
Distortion of the H2 O molecule

H2O, HF/6−31G** H2O, HF/6−31G**

94.3 107
oop
in−plane, ⊥ C2−axis oop
94.25 in−plane, || C2−axis 106.8 in−plane, ⊥ C2−axis
in−plane, || C2−axis
106.6
94.2

H−O−H angle [degrees]

106.4
d(O−H) [pm]

94.15
106.2
94.1
106

94.05
105.8

94 105.6

93.95 105.4
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
B [au] B [au]

I The molecule shrinks

I OH bonds contract by 0.25 pm in a field of 0.16 a.u.
I The molecule becomes more linear
I except for fields along the symmetry axis

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 18 / 22
Distortion of the NH3 molecule
I Magnetic field applied along the symmetry axis
NH3, HF/6−31G** NH3, HF/6−31G**
100.15 108.3

100.1
108.2

100.05
108.1
100

H−N−H angle [degrees]

108
99.95
d(N−H) [pm]

99.9 107.9

99.85
107.8

99.8
107.7
99.75

107.6
99.7

99.65 107.5
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
B [au] B [au]

I As expected the molecule shrinks

I bonds contract by 0.3 pm in a field of 0.15 a.u.

I Less intuitively, the molecule becomes more planar

I could this be caused by the shrinking lone pair?

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 19 / 22
Distortion of the C6 H6 molecule
I At B = 0.16, the molecule is 6.1 pm narrower and 3.5 pm longer in the field direction
I in agreement with perturbational estimates by Caputo and Lazzeretti, IJQC 111, 772 (2011)

C6H6, HF/6−31G*
107.6
C−H || B
C−H other
107.5

107.4

107.3

d(C−H) [pm]
107.2

107.1

107

106.9

106.8
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
B [au]

C6H6, HF/6−31G* C6H6, HF/6−31G*

138.75 120.5
C−C−C (a)
C−C−H (b)
138.7
120

138.65
119.5
138.6
bond angle [degrees]

C−C other (c)

d(C−C) [pm]

C−C || B (d) 119

138.55

138.5 118.5

138.45
118
138.4

117.5
138.35

138.3 117
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
B [au] B [au]
Linear response theory
I We have implemented linear response theory (RPA) in finite magnetic fields
I lowest CH3 radical states in magnetic fields (middle)
I transitions to the green state are electric-dipole allowed

I oscillator strength for transition to green CH3 state

I length (red) and velocity (blue) gauges

−39.25 0.07

−39.30 0.06
−39.35
0.05
−39.40
0.04
En [Ha]

f E1
−39.45
0.03
−39.50
0.02
−39.55

−39.60 0.01

−39.65 0.00
0.00 0.15 0.30 0.45 0.00 0.15 0.30 0.45
B⊥ [a.u.] B⊥ [a.u.]

Helgaker et al. (CTCC, University of Oslo) Molecules in strong magnetic fields 14th European Symposium on GED 21 / 22
Conclusions
I We have developed the LONDON program
I complex wave functions
I London atomic orbitals
I HF and FCI theories
I molecular gradients and linear response theory
I The LONDON program may be used for
I finite-difference alternative to analytical derivatives
I studies of molecules in strong magnetic fields
I studies of exchange–correlation functional in magnetic fields
I We have studied the behaviour of paramagnetic molecules in strong fields
I all paramagnetic molecules attain a global minimum at a characteristic field Bc
I Bc decreases with system size and should be observable for C72 H72
I We have studied H2 and He2 using FCI theory
I molecules become more strongly bound in magnetic fields
I the helium molecule becomes covalently bound

I We have studied molecular structure in magnetic fields

I bond distances are typically shortened in magnetic fields
I We have studied excitation energies in magnetic fields
I excitation energies typically increase in magnetic fields

Helgaker et al. (CTCC, University of Oslo) Conclusions 14th European Symposium on GED 22 / 22