2006 Summer School on Computational Materials Science Lecture Notes: Ab Initio Molecular Dynamics Simulation Methods in Chemistry
Victor S. Batista ^{∗}
Yale University, Department of Chemistry, P.O.Box 208107, New Haven, Connecticut 065208107, U.S.A.
I Introduction
These lectures will introduce computational methods that provide quantum mechanical descriptions of the dynamical and equilibrium properties of polyatomic systems. ^{1}^{–}^{7} According to the ﬁfth postulate of quantum mechanics, the description of dynamics requires solving the timedependent Schrodinger¨ equation
_{i}
∂Ψ _{t} (x)
∂t
^{=}
ˆ
HΨ _{t} (x),
(1)
subject to a given initial condition, Ψ _{0} (x). To keep the notation as simple as possible, all expressions are
written in atomic units, so = 1. Here, H = pˆ ^{2} /(2m) + V (ˆx) is the Hamiltonian operator, pˆ = −i∇ is the
momentum operator and V (ˆx) is the potential energy operator. A formal solution of Eq. (1) can be obtained by integration, as follows:
(2)
Ψ _{t} (x) = dx ^{} xe ^{−}^{i} ^{H}^{t} x ^{} x ^{} Ψ _{0} ,
ˆ
ˆ
ˆ
where the Kernel xe ^{−}^{i} ^{H}^{t} x ^{} is the quantum propagator. As an example, consider a diatomic molecule vibrating near its equilibrium position x¯ where the potential is Harmonic,
(3)
V (ˆx) = _{2} mω ^{2} (ˆx − x¯) ^{2} .
1
The description of the timedependent bondlength x(t) is given by the expectation value
x(t) = Ψ _{t} xˆΨ _{t} ,
(4)
where Ψ _{t} is deﬁned according to Eq. (2) with the particular Kernel,
xe ^{−}^{i} ^{H}^{t} x ^{} =
ˆ
mω 2π sinh(itω) ^{e}^{x}^{p} ^{−}
_{s}_{i}_{n}_{h}_{(}_{ω}_{i}_{t}_{)} mω [(x ^{2} + x ^{} ^{2} )cosh(ωit) − 2xx ^{} ] .
_{2}
(5)
This standard formulation of quantum mechanics relies upon the tools of calculus (e.g., derivatives, integrals, etc.) and involves equations and operations with inﬁnitesimal quantities as well as states in Hilbert space (the inﬁnite dimensional space of functions L ^{2} ). These equations, however, seldom can be solved analytically as shown in the example above. Therefore, computational solutions are necessary. However, computers can not handle inﬁnite spaces since they have only limited memory. In fact, all they can do is to store and manipulate discrete arrays of numbers. Therefore, the question is: how can we represent continuum states and operators in the space of memory of digital computers?
^{∗} Email: victor.batista@yale.edu
1
II
GridBased Representations
In order to introduce the concept of a gridrepresentation, we consider the state,
Ψ _{0} (x) = ^{α}
π
^{} 1/4 e _{−} _{α}
2
(x−x _{0} ) ^{2} +ip _{0} (x−x _{0} ) _{,}
_{(}_{6}_{)}
which can be expanded in the inﬁnite basis set of delta functions δ(x − x ^{} ) as follows,
Ψ _{0} (x) = dx ^{} c(x ^{} )δ(x − x ^{} ),
(7)
where c(x ^{} ) ≡ x ^{} Ψ _{0} = Ψ _{0} (x ^{} ). A gridbased representation of Ψ _{0} (x) can be obtained, in the coordinate range x = (x _{m}_{i}_{n} , x _{m}_{a}_{x} ), by discretizing Eq. (7) as follows,
(8)
n
Ψ _{0} (x) = ∆
c _{j} δ(x − x _{j} ),
j=1
where the array of numbers c _{j} ≡ x _{j} Ψ _{0} represent the state Ψ _{0} on a grid of equally spaced coordinates x _{j} = x _{m}_{i}_{n} + (j − 1)∆ with ﬁnite resolution ∆ = (x _{m}_{a}_{x} − x _{m}_{i}_{n} )/(n − 1). Note that the gridbased representation, introduced by Eq. (8), can be trivially generalized to a grid
etc.) when expanding
based representation in the multidimensional space of parameters ( e.g., x _{j} , p _{j} , γ _{j} ,
the target state Ψ _{0} (x) as a linear combination of basis functions xx _{j} , p _{j} , γ _{j} , with expansion coefﬁcients as c _{j} ≡ x _{j} , p _{j} , γ _{j} Ψ _{0} .
Problem 1: Write a Fortran code to represent the wavepacket, introduced by Eq. (6) on a grid. Visualize it with Gnuplot. Choose x _{0} = 0 and p _{0} = 0 , in the range x=(20,20), with α = ωm , where m = 1 and ω = 1 . If this is your ﬁrst Fortran code, copy the attached solution into a ﬁle named Problem1.f, compile it by typing f77 Problem1.f o Problem1, run it by typing ./Problem1, and visualize the output by ﬁrst typing gnuplot, and then typing plot “arch.0000”. Type quit, to exit Gnuplot.
Next, we consider gridbased representations in momentum space:
Ψ _{0} (p) = pΨ _{0} . 
(9) 

ˆ Inserting the closure relation 1 = ^{} dxx x in Eq. (9), we obtain that 

pΨ _{0} = dx px xΨ _{0} = (2π) ^{−}^{1}^{/}^{2} dxe ^{−}^{i}^{p}^{x} xΨ _{0} . 
(10) 

is the Fourier transform of the initial state since 

px = (2π) ^{−}^{1}^{/}^{2} e ^{−}^{i}^{p}^{x}^{ˆ} . 
(11) 
The Fourier transform can be efﬁciently implemented in O(N log(N )) steps, when xΨ _{0} is represented on
a grid with N = 2 ^{n} points (where n is an integer), by using the Fast Fourier Transform (FFT) algorithm. ^{8} In
contrast, the implementation of the Fourier transform by quadrature integration would require O(N ^{2} ) steps.
Problem 2: Write a Fortran code to represent the initial state, introduced by Eq. (6), in the momentum space by applying the FFT algorithm to the gridbased representation generated in Problem 1. Visualize the result with Gnuplot. Represent the wavepacket amplitudes and phases in the range p=(4,4) and compare
2
your output with the corresponding values obtained from the analytic Fourier transform obtained by using:
^{} dx
exp(−a _{2} x ^{2} + a _{1} x + a _{0} ) = ^{} π/a _{2} exp(a _{0} + a ^{2} /(4a _{2} )).
1
ˆ
Next, we consider the gridbased representation of operators ( e.g., xˆ , pˆ, V (ˆx), and T = pˆ ^{2} /(2m)) and
learn how these operators act on states represented on grids in coordinate and momentum spaces. Consider ﬁrst applying the potential energy operator to the initial state, as follows,
˜
V (ˆx)Ψ _{0} (x) = V (x)Ψ _{0} (x) ≡ Ψ _{0} (x).
Since Ψ _{0} (x) is just another function, Eq. (12) indicates that V (ˆx) can be represented on the same grid of
(12)
˜
coordinates as before ( i.e., equally spaced coordinates x _{j} = x _{m}_{i}_{n} + (j − 1)∆ , with ﬁnite resolution ∆ =
˜
(x _{m}_{a}_{x} − x _{m}_{i}_{n} )/(n − 1)). Since for each x _{j} , Ψ _{0} (x _{j} ) = V (x _{j} )Ψ(x _{j} ), the operator V (ˆx) can be represented just
as an array of numbers V (x _{j} ) associated with the gridpoints x _{j} , and its operation on a state is represented on such a grid as a simple multiplication.
Problem 3: Write a Fortran code to compute the expectation values of the position x(0) = Ψ _{0} xˆΨ _{0}
and the potential energy V = Ψ _{0} V (ˆx)Ψ _{0} , where V (x) is deﬁned according to Eq. (3) for the initial wave packet, introduced by Eq. (6), with various possible values of x _{0} and p _{0} , with α = ωm , where m = 1 and
ω = 1.
Now consider applying the momentum operator, pˆ = −i∇ , to the initial state Ψ _{0} (x) as follows,
(13)
One simple way of implementing this operation, when Ψ _{0} (x) is represented on a grid of equally spaced points x _{j} = x _{m}_{i}_{n} + (j − 1)∆ , is by computing ﬁniteincrement derivatives as follows:
G(x) = xpˆΨ _{0} = −i∇Ψ _{0} (x).
_{G}_{(}_{x} j _{)} _{=} _{−}_{i} Ψ _{0} (x _{j}_{+}_{1} ) − Ψ _{0} (x _{j}_{−}_{1} )
2∆
.
(14)
However, for a more general operator ( e.g., T = pˆ ^{2} /(2m)) this ﬁnite increment derivative procedure becomes complicated. In order to avoid computing ﬁniteincrement derivatives, one can implement an al
ternative procedure: represent the initial state in momentumspace (by Fourier transform of the initial state); apply the operator by simple multiplication in momentum space, then transform the resulting product back to the coordinate representation (by inverseFourier transform). This method can be derived by inserting the
ˆ
ˆ
closure relation 1 = ^{} dpp p, in Eq. (13),
G(x) = xpˆΨ _{0} = dp xpˆp pΨ _{0} = (2π) ^{−}^{1}^{/}^{2} dpe ^{i}^{p}^{x} p pΨ _{0} ,
(15)
since pΨ _{0} is deﬁned, according to Eq. (10), as the Fourier transform of the initial state. Note that the second equality of Eq. (15) is obtained by introducing the substitution
xp = (2π) ^{−}^{1}^{/}^{2} e ^{i}^{x}^{p}^{ˆ} .
(16)
While Eq. (15) illustrates the method for the speciﬁc operator pˆ, one immediately sees that any operator
which is a function of pˆ (e.g., T = pˆ ^{2} /(2m)) can be analogously applied according to the Fourier transform
procedure.
ˆ
Problem 4: Write a Fortran code to compute the expectation values of the initial momentum p(0) =
Ψ _{0} pˆΨ _{0} and the kinetic energy T = Ψ _{0} pˆ ^{2} /(2m)Ψ _{0} by using the Fourier transform procedure, where Ψ _{0} is the initial wavepacket introduced by Eq. (6), with x _{0} = 0, p _{0} = 0, and α = ωm , where m = 1 and
ω = 1. Compute the expectation value of the energy E = Ψ _{0}  HΨ _{0} , where H = pˆ ^{2} /(2m) + V (ˆx), with V (x)
deﬁned according to Eq. (3) and compare your result with the zeropoint energy E _{0} = ω/2 .
ˆ
ˆ
3
III
SOFT Method
The SplitOperator Fourier Transform (SOFT) method is a numerical approach for solving the time
dependent Schrodinger¨ equation by using gridbased representations of the timeevolving states and oper ators. It relies on the Fourier transform procedure, introduced in Sec. II, to apply operators that are functions of pˆ by simple multiplication of array elements. The essence of the method is to discretize the propagation time on a grid t _{k} = (k − 1)τ , with k = 1, and timeresolution τ = t/(n − 1), and obtain the wavepacket at the intermediate times t _{k} by recursively
, n
applying Eq. (2) as follows, Ψ t k+1 (x) = _{} dx xe −i
ˆ
^{H}^{τ} x ^{} x ^{} Ψ _{t} _{k} .
(17)
If τ is a sufﬁciently small timeincrement ( i.e., n is large), the timeevolution operator can be approximated according to the Trotter expansion to second order accuracy,
ˆ
_{e} −i Hτ _{=} _{e} −iV (ˆx)τ/2 _{e} −ipˆ ^{2} τ/(2m) _{e} −iV (ˆx)τ/2 _{+} _{O}_{(}_{τ} 3 _{)}_{,}
_{(}_{1}_{8}_{)}
which separates the propagator into a product of three operators, each of them depending either on xˆ , or pˆ.
Problem 5: Expand the exponential operators in both sides of Eq. (18) and show that the Trotter expan sion is accurate to second order in powers of τ .
ˆ
Substituting Eq. (18) into Eq. (17) and inserting the closure relation 1 = ^{} dpp p gives,
_{Ψ} _{t} k+1 _{(}_{x}_{)} _{=} ^{} _{d}_{p} ^{}
_{d}_{x} _{e} −iV (ˆx)τ/2 _{} _{x}_{}_{p} _{} _{e} −ip ^{2} τ/(2m) _{} _{p}_{}_{x} _{} _{e} −iV (x ^{} )τ/2 _{Ψ} _{t} k _{(}_{x} _{)}_{.}
_{(}_{1}_{9}_{)}
By substituting px ^{} and xp according to Eqs. (11) and (16), respectively, we obtain:
_{Ψ} t k+1 _{(}_{x}_{)} _{=} _{e} −iV (ˆx)τ/2
^{1}
2π
√
_{d}_{p}_{e} ixp _{e} −ip ^{2} τ/(2m)
^{1}
2π ^{}
√
_{d}_{x} _{e} −ipx ^{} _{e} −iV (x ^{} )τ/2 _{Ψ} _{t} k _{(}_{x} _{)}_{.}
_{(}_{2}_{0}_{)}
According to Eq. (20), then, the computational task necessary to propagate Ψ _{t} (x) for a timeincrement τ involves the following steps:
1. Represent Ψ _{t} _{k} (x ^{} ) and e ^{−}^{i}^{V} ^{(}^{x} ^{} ^{)}^{τ}^{/}^{2} as arrays of numbers Ψ _{t} _{k} (x _{j} ) and e ^{−}^{i}^{V} ^{(}^{x} ^{j} ^{)}^{τ}^{/}^{2} associated with a grid of equally spaced coordinates x _{j} = x _{m}_{i}_{n} + (j − 1)∆ , with ﬁnite resolution ∆ = (x _{m}_{a}_{x} − x _{m}_{i}_{n} )/(n − 1).
2. Apply the potential energy part of the Trotter expansion e ^{−}^{i}^{V} ^{(}^{x} ^{} ^{)}^{τ}^{/}^{2} to Ψ _{t} _{k} (x ^{} ) by simple multiplication of array elements:
˜
˜
_{Ψ} t k _{(}_{x} j _{)}
˜
_{=} _{e} −iV (x _{j} )τ/2 _{Ψ} t k _{(}_{x} j _{)}_{.}
3. Fourier transform Ψ _{t} _{k} (x _{j} ) to obtain Ψ _{t} _{k} (p _{j} ), and represent the kinetic energy part of the Trotter expan
2
sion e ^{−}^{i}^{p} ^{2} ^{τ}^{/}^{(}^{2}^{m}^{)} as an array of numbers e ^{−}^{i}^{p} ^{τ}^{/}^{(}^{2}^{m}^{)} associated with a grid of equally spaced momenta p _{j} = j/(x _{m}_{a}_{x} − x _{m}_{i}_{n} ).
j
4. Apply the kinetic energy part of the Trotter expansion e ^{−}^{i}^{p} ^{2} ^{τ}^{/}^{(}^{2}^{m}^{)} to the Fourier transform Ψ _{t} _{k} (p) by
˜
simple multiplication of array elements:
Ψ _{t} _{k} (p _{j} ) = e ^{−}^{i}^{p}
2
j
τ/(2m)
˜
Ψ _{t} _{k} (p _{j} ).
5. Inverse Fourier transform Ψ _{t} _{k} (p _{j} ) to obtain Ψ _{t} _{k} (x _{j} ) on the grid of equally spaced coordinates x _{j} .
4
6. Apply the potential energy part of the Trotter expansion e ^{−}^{i}^{V} ^{(}^{x} ^{} ^{)}^{τ}^{/}^{2} to Ψ _{t} _{k} (x ^{} ) by simple multiplication of array elements,
Ψ t k+1 (x j ) = e −iV (x j )τ/2
Ψ _{t} _{k} (x _{j} ).
Problem 6: Write a Fortran code that propagates the initial state Ψ _{0} (x) for a single time increment
(τ = 0.1 a.u.). Use x _{0} = −2.5 , p _{0} = 0, and α = ωm , where m = 1 and ω = 1. Implement the SOFT method
for the Hamiltonian H = pˆ ^{2} /(2m) + V (ˆx), where V (x) is deﬁned according to Eq. (3). Compare the resulting
propagated state with the analytic solution obtained by substituting Eq. (5) into Eq. (2).
ˆ
Problem 7: Loop the Fortran code developed in Problem 5 with x _{0} = −2.5 and p _{0} = 0 for 100 steps with τ = 0.1 a.u. For each step compute the expectation values of coordinates x(t) and momenta p(t) as done in Problems 3 and 4, respectively. Compare your calculations with the analytic solutions obtained by substituting Eq. (5) into Eq. (2). Verify that these correspond to the classical trajectories x(t) = x¯ + (x _{0} − x¯)cos(ωt) and p(t) = p _{0} − (x _{0} − x¯)ωm sin(ωt), which can be computed according to the VelocityVerlet algorithm:
^{(}^{2}^{1}^{)}
x _{j}_{+}_{1} = x _{j} + p _{j} τ /m + F (x _{j} )τ ^{2} /(2m).
p _{j}_{+}_{1} = p _{j} + (F(x _{j} ) + F(x _{j}_{+}_{1} ))τ /2
Problem 8: Change the potential to that of a Morse oscillator V (ˆx) = De(1 − exp(−a(ˆx − x _{e} ))) ^{2} , with
x _{e} = 0, De = 8, and a = ^{} k/(2D _{e} ), where k = mω ^{2} . Recompute the wavepacket propagation with x _{0} = −0.5 and p _{0} = 0 for 100 steps with τ = 0.1 a.u., and compare the expectation values x(t) and p(t) with the corresponding classical trajectories obtained by recursively applying the VelocityVerlet algorithm.
Problem 9: Simulate the propagation of a wavepacket with x _{0} = −5.5 and initial momentum p _{0} = 2 colliding with a barrier potential V (x) = 3 , if abs(x) < 0.5 , and V (x) = 0 , otherwise. Hint: In order to avoid artiﬁcial recurrences you might need to add an absorbing imaginary potential V _{a} (x) = i(abs(x) − 10) ^{4} , if abs(x) > 10, and V _{a} (x) = 0 , otherwise.
IV SOFT Propagation on Multiple Surfaces
The goal of this section is to generalize the implementation of the SOFT method to the description of quantum dynamics on multiple coupled potential energy surfaces. To keep the presentation as simple as possible, we consider a molecule with twocoupled electronic states described by the Hamiltonian,
H ˆ = pˆ ^{2} /(2m) + V ,
(22)
ˆ
ˆ
ˆ
ˆ
ˆ
ˆ
where V = V _{0} + V _{c} , with V _{0} = V _{1} (xˆ)1 1 + V _{2} (xˆ)2 2 and V _{c} = V _{c} (xˆ)1 2 + V _{c} (xˆ)2 1.
The computational task ahead is to implement the SOFT method to compute the timedependent wave packet
(23)
given the initial conditions ϕ _{1} (x; 0) and ϕ _{2} (x; 0) , where ϕ _{1} (x; t) and ϕ _{2} (x; t) are the timedependent nuclear wavepacket components associated with the electronic states 1 and 2 , respectively. Note that here the
Ψ(x; t) = ϕ _{1} (x; t)1 + ϕ _{2} (x; t)2 ,
ˆ
ˆ
ˆ
main challenges are that V _{0} and V _{c} do not commute, Ψ(x; t) involves two wavepacket components and H
is a 2 × 2 matrix in the basis of 1 and 2 .
5
A simple approach for propagating ϕ _{1} (x; t) and ϕ _{2} (x; t) involves the embedded form of the Trotter ex
pansion,
ˆ
_{e} −i H2τ _{≈} _{e} −i _{2}_{m} τ _{e} −iV (xˆ)2τ _{e} −i _{2}_{m} τ _{≈} _{e} −i _{2}_{m} τ _{e} −iV _{0} (xˆ)τ _{e} −iV _{c} (xˆ)2τ _{e} −iV _{0} (xˆ)τ _{e} −i
pˆ ^{2}
pˆ ^{2}
pˆ ^{2}
pˆ ^{2}
2m ^{τ} ,
(24)
which can be implemented in the basis of 1 and 2 according to the following steps:
• Step [I]. Apply the kinetic energy part of the Trotter expansion to both wavepacket components ϕ _{1} (x; t) and ϕ _{2} (x; t) for time τ , as follows,
2
^{} ϕ ^{} (x; t + τ)
ϕ _{2} ^{} (x; t + τ) ^{=} e −i
1
pˆ
2m ^{τ}
0
_{0}
e ^{−}^{i}
2
pˆ
2m τ
^{} ϕ _{1} (x; t)
t)
ϕ _{2} (x;
• Step [II]. Mix the two wavepacket components ϕ ^{} _{1} (x; t + τ ) and ϕ _{2} ^{} (x; t + τ),
with
^{} _{ϕ}
_{ϕ}
1
2
(x; t + τ)
(x; t
+ τ) ^{=} ^{M}
M ≡ L −1 ^{} _{e} −iE _{1} (x)τ
_{0}
ϕ _{1} ^{} (x; t + τ) ϕ _{2} ^{} (x; t + τ)
,
_{0}
_{e} −iE _{2} _{(}_{x}_{)}_{τ}
L,
. 
(25) 
(26) 

(27) 
where E _{1} (x) and E _{2} (x) are the eigenvalues of the potential energy matrix V = V _{0} +V _{c} and L the matrix of column eigenvectors in the basis of diabatic states 1 and 2 . Eigenvalues and eigenvectors of a symmetric matrix can be obtained by using the subroutines TRED2, TQLI and EIGSRT, as described in Numerical Recipes (Chapter 11). ^{9}
While this is a general procedure, the speciﬁc case of interest involves a 2 × 2 Hermitian matrix V , for which the matrix M can be found analytically,
M ≡
_{e}
−i
ˆ
^{V} ^{1} ^{(}^{x}^{ˆ}^{)}^{2}^{τ} cos (2V _{c} (xˆ)τ )
−i sin (2V _{c} (xˆ)τ) e ^{−}^{i}^{(}
ˆ
V _{1} (xˆ)+
ˆ
^{V} ^{2} ^{(}^{x}^{ˆ}^{)}^{)}^{τ}
ˆ
ˆ
−i sin(2V _{c} (xˆ)τ) e ^{−}^{i}^{(} cos (2V _{c} (xˆ)τ) e ^{−}^{i}
ˆ
V _{1} (xˆ)+ V _{2} (xˆ))τ
V _{2} (xˆ)2τ
.
(28)
• Step [III]. Propagate ϕ ^{}^{} (x; t + τ ) and ϕ ^{}^{} (x; t + τ ) for time τ , according to the freeparticle propagator, by applying the kinetic energy part of the Trotter expansion:
1
2
^{}
ϕ
ϕ _{2} (x; t + 2τ) ^{=} e −i
1
(x; t + 2τ)
2
0
pˆ
2m ^{τ}
_{0}
e ^{−}^{i}
2
pˆ
2m τ
_{ϕ}
_{ϕ}
1
2
(x; t + τ)
(x; t
τ)
+
^{.}
^{(}^{2}^{9}^{)}
In practice, however, step [III] is combined with step [I] of the next propagation timeslice for all but the last propagation timeincrement.
Problem 10: (a) Derive Eq. (28) by considering that,
^{w}^{i}^{t}^{h}
e −iV c 2τ = D † ^{} _{e} iV _{c} (x)2τ
_{0}
_{D} _{=} _{D} _{†} _{≡} ^{} −1/ ^{√} 2
1/ ^{√} 2
6
_{0}
_{e} −iV _{c} _{(}_{x}_{)}_{2}_{τ}
1/
1/ ^{√} _{2} ^{,}
2
^{√}
D, 
(30) 
(31) 
since
and
with DD ^{†} = 1.
1
e ^{−}^{i}^{V} ^{c} ^{2}^{τ} = 1 + (−iV _{c} 2τ) + _{2}_{!} (−iV _{c} 2τ) ^{2} +
V _{c} ≡ _{}
0
V _{c} (x)
V _{c} (x)
0
^{} _{=} _{D} _{†} ^{} −V _{c} (x)
0
V _{c}
0
_{(}_{x}_{)}
,
D,
(32)
(33)
Problem 11: Derive Eq. (27) by writing the matrix V in the basis of adiabatic eigenstates
φ _{1} (x) 
= 
L _{1}_{1} (x)1 + 
L _{2}_{1} (x)2 , 
φ _{2} (x) = L _{1}_{2} (x)1 + 
L _{2}_{2} (x)2 , 
(34)
with eigenvalues E _{1} (x) and E _{2} (x), respectively. Then, using the expansion
1
e ^{−}^{i}^{V}^{2}^{τ} = 1 + (−iV2τ) + _{2}_{!} (−iV2τ) ^{2} +
show that in the adiabatic representation
e −iV2τ = ^{} _{e} −iE _{1} (x)2τ
_{0}
_{0}
_{e} −iE _{2} (x)2τ
^{.}
,
(35)
^{(}^{3}^{6}^{)}
Finally, show that the diagonal matrix introduced by Eq. (36) can be rotated to the representation of diabatic states 1 , 2 according to the similarity transformation
L −1 ^{} _{e} −iE _{1} (x)τ
0
0
_{e} −iE _{2} (x)τ
^{L}^{.}
^{(}^{3}^{7}^{)}
Problem 12: (a) Write a Fortran code to implement the SOFT approach described in this section, where step [II] is numerically computed according to Eq. (27). Propagate Ψ(x; t) = ϕ _{1} (x; t)1 +ϕ _{2} (x; t)2 , where ϕ _{1} (x; 0) = ϕ _{1} (x; 0) = Ψ _{0} (x) and Ψ _{0} (x) as deﬁned in Eq. (6). Use x _{0} = −2.2 , p _{0} = 0, m = 1, ω = 1 and two coupled potential energy surfaces described by the potential energy matrix
_{V}
_{=} ^{} V _{1} (x) δ
V _{2}
δ
_{(}_{x}_{)}
,
(38)
where δ = 0.3 , V _{1} (x) = mω ^{2} (x − x¯) ^{2} /2 and V _{2} (x) = −x ^{2} /2 + x ^{4} /22 ; (b) Propagate Ψ(x; t) according to the potential energy matrix introduced by Eq. (38), with δ = 0 and compare your results with those obtained in item (a)
V Matching Pursuit Representation
The goal of this section is to generalize the gridbased representation of states, introduced in Sec. II, to representations generated according to the matchingpursuit algorithm as implemented for overcomplete basis sets of nonorthogonal basis functions. The main advantage of overcomplete basis sets is that they provide nonunique representations, since there are multiple ways of expanding a target state as a linear combination of nonorthogonal basis func tions ( i.e, basis functions that can be expanded as linear combinations of the other basis functions in the
7
set). Therefore, one can deﬁne expansions that exploit the beneﬁt of nonuniqueness in order to simulta neously achieve sparsity (i.e., representations with the fewest possible signiﬁcant terms), superresolution (i.e., a resolution that is higher than that possible with traditional nonadaptive methods) and speed (i.e., representations obtainable in O(n) or O(n log(n) steps, where n is the number of basis functions in the basis set. The matching pursuit method implements a greedy algorithm for representing a target state (wavefunc tion) by successive orthogonal projections onto elements of an overcomplete basis set as follows: The ﬁrst step requires selecting the basis element  1 that has maximum overlap with the target state  Ψ _{t} (i.e., the element that is resonant with the most prominent structure in  Ψ _{t} ). The projection of such element is deﬁned as follows:
(39)
Ψ _{t} = c _{1} 1 + ε _{1} ,
where c _{1} ≡ 1Ψ _{t} . Note that by virtue of the deﬁnition of c _{1} the residual vector ε _{1} is orthogonal to 1 . Therefore, Ψ _{t} < ε _{1} . The next step involves the subdecomposition of the residual vector ε _{1} by project ing it along the direction of its best match 2 as follows:
(40)
ε _{1} = c _{2} 2 + ε _{2} ,
where c _{2} ≡ 2ε _{1} . Note that, since ε _{2} is orthogonal to 2 , the norm of ε _{2} is smaller than the norm of ε _{1} . This procedure is repeated each time on the resulting residue. After n successive orthogonal projections, the norm of the residual vector ε _{n} is smaller than a desired precision . Therefore, the algorithm maintains norm conservation within a desired precision,
ε _{n} = 1 −
n
j=1
c _{j}  ^{2} < ,
(41)
just as in a linear orthogonal decomposition. The resulting expansion is
xΨ _{t} ≈
n
j=1
c _{j} xj ,
(42)
where the coefﬁcients c _{j} are recursively deﬁned as follows:
c _{j} = jΨ _{t} −
j−1
k=1
c _{k} jk .
(43)
Matching pursuit coherentstate expansions can be obtained by successively selecting the basis func tions according to a gradientbased optimization technique. ^{1}^{0} A parallel implementation under the Message Passing Interface (MPI) environment ^{1}^{1} can speed up the search for a satisfactory local minimum. Starting from an initial trial coherent state χ _{j} , we can optimize the parameters x _{j} (k), p _{j} (k) and γ _{j} (k) so that they locally maximize the overlap with the target state. Initial guess parameters γ _{j} (k), x _{j} (k) and p _{j} (k) can be chosen as deﬁned by the basis elements of the previous wavepacket representation (or initial state).
Problem 13: Write a Fortran code to represent the target state
_{Ψ} ˜ _{0} _{(}_{x}_{)} _{≡} _{e} −ipˆ ^{2} /(2m)τ/2 _{e} −iV (x)τ _{e} −ipˆ ^{2} /(2m)τ/2 _{Ψ} _{0} _{(}_{x}_{)}_{,}
where τ = 0.1 a.u. and V (x) is deﬁned as in Problem 6, as a matching pursuit expansion based on coherent states x _{j} , p _{j} , γ _{j} parametrized as follows:
xx _{j} , p _{j} , γ _{j} = ^{γ} ^{j}
π ^{} 1/4 e
8
− ^{γ} ^{j}
2
(x−x _{j} ) ^{2} +ip _{j} (x−x _{0} ) _{.}
_{(}_{4}_{4}_{)}
VI
MP/SOFT Method for Adiabatic Propagation
The goal of this section is to introduce the implementation of the SOFT method for adiabatic quantum propagation, described in Sec. III, in terms of dynamically adaptive coherentstate representations gener ated according to the matchingpursuit algorithm introduced in Sec. V. In order to implement the Trotter expansion,
pˆ
2
_{(}_{4}_{5}_{)}
by using representations based on matchingpursuit coherentstate expansions, one can proceed according to the following steps:
• Step 1. Decompose the target function Ψ _{t} (x) ≡ e ^{−}^{i}^{V} ^{(}^{x}^{ˆ}^{)}^{τ}^{/}^{2} Ψ _{t} (x) into matching pursuit coherent state
Ψ _{t}_{+}_{τ} (x) = e ^{−}^{i}^{[}
_{2}_{m} +V (xˆ)]τ _{Ψ} t _{(}_{x}_{)} _{≈} _{e} −iV (xˆ)τ/2 _{e} −ipˆ ^{2} /(2m)τ _{e} −iV (xˆ)τ/2 _{Ψ} t _{(}_{x}_{)}_{,}
˜
expansions,
˜
Ψ _{t} (x) ≈
n
c _{j} xχ _{j} .
(46)
j=1
Here, xχ _{j} are N dimensional coherent states,
N
xχ _{j} ≡ k=1 A _{j} (k)exp − ^{γ} ^{j} ^{(}^{k}^{)} (x(k) − x _{j} (k)) ^{2} + ip _{j} (k)(x(k) − x _{j} (k)) ,
2
(47)
where A _{j} (k) are normalization factors and γ _{j} (k), x _{j} (k) and p _{j} (k) are complexvalued parameters selected according to the matching pursuit algorithm. The expansion coefﬁcients c _{j} , introduced by
Eq. (46), are deﬁned before: c _{1} ≡ χ _{1} Ψ _{t} , and c _{j} ≡ χ _{j} Ψ _{t} − ^{} ^{j}^{−}^{1} _{k}_{=}_{1} c _{k} χ _{j} χ _{k} , for j = 2– N .
˜
• Step 2. Apply the kinetic energy part of the Trotter expansion to Ψ _{t} (x) by Fourier transforming the
˜
coherent state expansion of Ψ _{t} (x) to the momentum representation, multiplying it by exp[−i(p ^{2} /2m)τ]
and ﬁnally computing the inverse Fourier transform of the product to obtain:
n
(48)
Ψ _{t} (x) =
c _{j} xχ˜ _{j} ,
j=1
where
m + iτ γ _{j} (k) ^{e}^{x}^{p}
N xχ˜ _{j} ≡ k=1 A _{j} (k)
m
_{(}_{k}_{)} − i[x _{j} (k) − x(k)] ^{2}
^{} p _{j} (k)
γ
j
2
γ
j
(k)
^{+} ^{2}^{i}^{τ}
m
The resulting timeevolved wavefunction is thus
n
Ψ _{t}_{+}_{τ} (x) =
j=1
c _{j} e ^{−}^{i}^{V} ^{(}^{x}^{)}^{τ}^{/}^{2} xχ˜ _{j} ,
_{−}
p _{j} (k) 2γ _{j} (k)
_{} _{.}
(49)
(50)
which can be reexpanded in coherent states as in step [1].
Note that the underlying computational task necessary for MP/SOFT quantum propagation is completely reduced to generating the coherentstate expansions deﬁned by Eq. (46), since all of the other steps can be implemented analytically.
Problem 14: Note that the Fortran code developed in Problem 13 already implements the MP/SOFT
method described in this section, as applied to the Harmonic potential of Problem 5. Now, loop the code for 100 steps and make the comparison between numerical and analytical results for the whole propagation
time. Use (τ = 0.1 a.u.)
with x _{0} = −2.5 , p _{0} = 0, and α = ωm , where m = 1 and ω = 1.
9
VII
MP/SOFT Simulations of Nonadiabatic Dynamics in Pyrazine
MP/SOFT simulations of nonadiabatic dynamics can be efﬁciently performed according to the SOFT method outlined in Sec. IV, in conjunction with the matchingpursuit representation method introduced in Sec. V. The goal of this section is to illustrate the resulting approach as applied to the description of the S _{1} /S _{2} interconversion of pyrazine after S _{0} → S _{2} photoexcitation. The photophysics of pyrazine provides a standard platform for study ultrafast internal conversion responsible for a broad band photoabsorption spec trum with a rather diffuse superimposed structure. The underlying excited state nonadiabatic dynamics, following S _{0} → S _{1} (π, π ^{∗} ), S _{2} (n, π ^{∗} ) photoexcitation, is also ideally suited to benchmark the capabilities of new theoretical methods since it has been extensively investigated both experimentally ^{1}^{2}^{,} ^{1}^{3} and theoreti cally. ^{1}^{4}^{–}^{2}^{0} Ab initio calculations have characterized the existence of a conical intersection between the S _{1} and S _{2} states, leading to ultrafast intramolecular energy transfer. ^{1}^{4} The experimental S _{2} photoabsorption spectrum has been reproduced by using a 4mode model Hamiltonian, after convoluting the resulting spec trum with an experimental resolution function, ^{2}^{1} or explicitly including the effect of the remaining vibrational modes as a weakly coupled harmonic bath. ^{1}^{5} These two models have allowed for direct comparisons be tween benchmark calculations and stateoftheart semiclassical and quantum mechanical methods, includ ing the multiconﬁgurational time dependent Hartree (MCTDH) approach, ^{1}^{5} the Herman Kluk semiclassical initial value representation (SC IVR) method, ^{1}^{7} the multiple spawning quantum approach, ^{1}^{8} the time depen dent GaussHermite discrete value representation (TDGHDVR) method, ^{1}^{9} and the coupled coherent states (CCS) technique. ^{2}^{0} Here, the capabilities of the generalized MP/SOFT approach are evaluated as applied to the description of the photoabsorption spectroscopy of pyrazine. The problem concerns the propagation of the wavepacket components ϕ
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