text:
# Computing characteristic classes of projective schemes

## 1. Introduction

### 1.1.

In this article we describe an algorithm computing, among other things, the topological Euler characteristic of the support of a projective scheme $`S`$ over $``$. In fact, we will compute the push-forward to $`^n`$ of the Chern-Schwartz-MacPherson class $`c_{\text{SM}}(S)`$ of the support of $`S`$, given the ideal $`I`$ of $`S`$ in $`^n`$; as is well known, the Euler characteristic equals the degree of the component of dimension 0 of $`c_{\text{SM}}(S)`$. We also include a computation of the push-forward of the (Chern-)Fulton class $`c_\text{F}(S)`$ of $`S`$; when $`S`$ is nonsingular, this provides a different way to compute the Euler characteristic of $`S`$.

Other algorithms computing the Euler characteristic of a (possibly singular) scheme are somewhat indirect (see Uli Walther’s contribution to \[EGSS02\], as well as \[Wal01\]). The nonsingular case can be treated by computing the Hodge numbers $`h^{ij}`$. Even in the nonsingular case, however, we are not aware of algorithms yielding (the degrees of) the Chern classes of $`S`$; for a nonsingular variety, the outputs of our algorithms for $`c_{\text{SM}}(S)`$ and $`c_\text{F}(S)`$ coincide, and consist precisely of this information.

### 1.2.

The main ingredients to our algorithms are the results of \[Alu99\] and \[Alu\], and explicit computations of Segre classes. The considerations in \[Alu\] reduce the problem of the computation of $`c_{\text{SM}}(S)`$, for $`S^n`$, to the case in which $`S`$ is a hypersurface in $`^n`$; the main result of \[Alu99\] translates this case to the computation of a Segre class; and a close look at Segre classes in $`^n`$ reveals that tools such as Macaulay2 (\[GS\]) are capable of computing them.

In fact the ability to compute Segre classes appears to us of independent interest, for example in view of potential applications to enumerative geometry. An immediate application to characteristic classes yields the Fulton class $`c_\text{F}(S)`$ of $`S`$ (term by which we refer to the class introduced by William Fulton in \[Ful84\], Example 4.2.6(a)).

### 1.3.

The article is organized as follows. In §2 we describe the algorithm computing $`c_{\text{SM}}(S)`$, and hence $`\chi (S)`$. We have given this discussion a prominent place since it may be the item of more immediate interest in the paper; but in fact at one key step in the proof of the main result in §2, and in the resulting algorithm, we will borrow some material from the following §3. The algorithm is summarized in §2.6. We end §2 by pointing out that judicious use of the algorithm yields the computation of Euler characteristics of affine schemes (over a field) as well—and hence in principle of arbitrary schemes, as every scheme is the disjoint union of affine ones.

In §3 we discuss the problem of computing more general Segre classes. Serious applications are so far severely limited by technological constraints. However, one subproduct of the discussion in §3 is the algorithm giving Fulton class.

Several concrete examples are given in §4. Among these, we mention the computation of Milnor classes of a projective scheme, as these have been the subject of rather intense work in recent years. Briefly, the Milnor class measures the difference between Chern-Schwartz-MacPherson and Fulton classes of a singular variety. For complete intersections, Shoji Yokura (\[Yok99a\]) has identified the computation of these classes as a Verdier-Riemann-Roch type problem. The most general results obtained in this direction are in the recent \[Sch\]; for surveys of work on Milnor classes, see \[Yok99b\] and \[Bra00\].

### 1.4.

We have implemented the algorithms described in this paper in Macaulay2. Our code (and, we hope, future improvements) is available at

http://www.math.fsu.edu/~aluffi/CSM/CSM.html

In any case, the reader should have no difficulties translating the discussion presented in this paper into working routines in Macaulay2 or other commutative algebra/algebraic geometry symbolic packages.

Acknowledgments I thank the Max-Planck-Institut für Mathematik in Bonn, Germany, for the hospitality and support, and Florida State University for granting a sabbatical leave in 2001-2.

## 2. Chern-Schwartz-MacPherson classes and the Euler characteristic

### 2.1.

Throughout the paper, $`i:S^n=^nk`$ will denote a closed embedding; in this section $`k`$ will be a field of characteristic 0. We will let $`I=k[z_0,\mathrm{},z_n]`$ be a homogeneous ideal defining $`S`$.

The output of our computations will be classes in the Chow group of $`^n`$. Denoting by $`H`$ the hyperplane class, this is $`[H]/(H^{n+1})`$: classes in $`^n`$ will be written as polynomials of degree $`n`$ in $`H`$, with integer coefficients:

$$a_0+a_1H+\mathrm{}+a_nH^n.$$

The degree of a class, denoted $``$, will be the coefficient of $`H^n`$ in such an expression.

### 2.2.

If $`S`$ is a nonsingular variety, we may consider its (total, homology) Chern class $`c(TS)[S]`$. Chern-Schwartz-MacPherson classes provide a notion agreeing with $`c(TS)[S]`$ when $`S`$ is nonsingular, but defined regardless of the nonsingularity of $`S`$. Further, they satisfy a clever functorial prescription, which we quickly summarize.

Denote by $`c_{\text{SM}}(S)`$ the Chern-Schwartz-MacPherson class of $`S`$, and extend this definition to constructible functions by setting

$$c_{\text{SM}}(\underset{VS}{}m_V11_V)=\underset{V}{}m_Vc_{\text{SM}}(V).$$

Here the sum is finite, $`V`$ are closed subvarieties of $`S`$, $`m_V`$, and $`11_V`$ denotes the function that is $`1`$ along $`V`$ and $`0`$ outside of $`V`$. This defines a homomorphism of abelian groups $`𝒞(S)𝒜(S)`$ for every $`S`$, where $`𝒞`$, $`𝒜`$ denote respectively the functor of constructible functions (with push-forward defined by Euler characteristic of fibers) and the Chow group functor. But in fact

$$c_{\text{SM}}:𝒞𝒜$$

defines a natural transformation: this was proved by Robert MacPherson in the article where the classes are introduced. For MacPherson’s construction of $`c_{\text{SM}}`$, and for more information, we address the reader to the original \[Mac74\], or to \[Ken90\] (extending the theory to arbitrary algebraically closed field of characteristic 0); and to \[Bra00\] for a comparison with the different approach of Marie-Hélène Schwartz, in fact predating MacPherson’s work. Regardless of the approach, at the moment the theory of Chern-Schwartz-MacPherson classes has only been studied in characteristic $`0`$, and this is why we assume that our ground field is of characteristic $`0`$ in this section.

### 2.3.

In fact, the theory is usually only applied to reduced schemes. More generally, we take $`c_{\text{SM}}(S)`$ to be the Chern-Schwartz-MacPherson class of the support $`S_{\text{red}}`$ of $`S`$. As a very particular case of the functoriality of Chern-Schwartz-MacPherson classes, consider the constant map on a proper scheme $`S`$,

$$\kappa :S\text{point}.$$

Then the covariance of $`c_{\text{SM}}`$ for $`\kappa `$ amounts to

$$\kappa _{}c_{\text{SM}}(S)=c_{\text{SM}}(\kappa _{}11_S)=c_{\text{SM}}(\chi (S_{\text{red}})11_{\text{point}})=\chi (S_{\text{red}})[\text{point}],$$

and in particular

$$c_{\text{SM}}(S)=\chi (S_{\text{red}}).$$

With $`S`$ projective, and $`i:S^n`$ a closed embedding, this says that

$$\chi (S_{\text{red}})=i_{}c_{\text{SM}}(S):$$

that is, the topological Euler characteristic of the support of $`S`$ equals the coefficient of $`H^n`$ in

$$i_{}c_{\text{SM}}(S)=c_0+c_1H+\mathrm{}+c_nH^n.$$

Computing this class is our main goal.

We note in passing that the computations we will describe can all be performed over any field over which $`S`$ is defined. Thus, a tool such as Macaulay2 will be able to compute the topological Euler characteristic of a scheme $`S^n`$ by working over $``$ (for example), so long as $`S`$ is in fact defined over $``$.

### 2.4.

We will now describe a procedure computing $`i_{}c_{\text{SM}}(S)`$, given a homogeneous ideal

$$I=(F_1,\mathrm{},F_r)$$

defining $`S`$ in $`^n`$. Write

$$S=X_1\mathrm{}X_r$$

where $`X_i`$ is the hypersurface defined by $`F_i`$. Applying ‘inclusion-exclusion’, it suffices then (see \[Alu\]) to compute $`i_{}c_{\text{SM}}(X)`$ for $`X`$ ranging over the unions $`X_{i_1}\mathrm{}X_{i_s}`$, $`1sr`$. In other words, the problem of computing $`i_{}c_{\text{SM}}(S)`$ is readily reduced to the computation of $`i_{}c_{\text{SM}}(X)`$ for $`X`$ a hypersurface in $`^n`$.

If $`X`$ is a hypersurface, the computation of $`c_{\text{SM}}(X)`$ is reduced to the computation of the Segre class of the singularity subscheme of $`X`$ by the main result of \[Alu99\]. The form taken by this result when the ambient nonsingular variety is projective space is the following.

### 2.5.

Let $`X^n`$ be a hypersurface, with homogeneous ideal $`(F)k[z_0,\mathrm{},z_n]`$. Consider the rational map

$$^n^N=^n$$

defined by

$$p(\frac{F}{z_0}_{|_p}:\mathrm{}:\frac{F}{z_n}_{|_p}).$$

We let $`\mathrm{\Gamma }`$ be the (closure of the) graph of this map. Viewing $`^n\times ^N`$ as a $`^N`$-bundle over $`^n`$, we are interested in what we elsewhere call the shadow of the class of $`\mathrm{\Gamma }`$: that is, letting $`K`$ be the pull-back of the hyperplane class from $`^N`$, the class

$$G=g_0+g_1H+\mathrm{}+g_nH^n$$

in $`A_{}^n`$, where $`g_i`$ is the degree of the image in $`^n`$ of $`K^i[\mathrm{\Gamma }]`$.

###### Theorem 2.1.

With the notations introduced above,

$$i_{}c_{\text{SM}}(X)=(1+H)^{n+1}\underset{i=0}{\overset{n}{}}g_d(H)^d(1+H)^{nd}.$$

###### Proof.

By Theorem I.4 in \[Alu99\],

$$i_{}c_{\text{SM}}(X)=c(T^n)i_{}\left(s(X,^n)+c(𝒪(X))^1\left(s(Y,^n)^{}𝒪(X)\right)\right)$$

where $`Y`$ denotes the singularity subscheme of $`X`$; this is the scheme defined by the vanishing of the partials of $`F`$. By Proposition 3.1 in the next section, $`i_{}s(Y,^n)`$ can be recovered from the class $`G=g_0+g_1H+\mathrm{}+g_nH^n`$:

$$i_{}s(Y,^n)=1c(𝒪(dH))^1\left(G𝒪(dH)\right),$$

where $`d=\mathrm{deg}X1`$ (so $`𝒪(X)=𝒪((d+1)H)`$).

The manipulations massaging this formula into the one given in the statement are streamlined by using Proposition 1 in \[Alu94\]:

$$i_{}s(Y,^n)^{}=1c(𝒪(dH))^1\left(G^{}𝒪(dH)\right)$$

$$i_{}s(Y,^n)^{}𝒪(X)=1\frac{c(𝒪(X))}{c(𝒪(H))}\left(G^{}𝒪(H)\right)$$

$$c(𝒪(X))^1\left(i_{}s(Y,^n)^{}𝒪(X)\right)=c(𝒪(X))^1c(𝒪(H))^1\left(G^{}𝒪(H)\right),$$

and hence

$`i_{}c_{\text{SM}}(X)`$ $`=(1+H)^{n+1}\left(c(𝒪(X))^1[X]+c(𝒪(X))^1c(𝒪(H))^1\left(G^{}𝒪(H)\right)\right)`$
$`=(1+H)^{n+1}(1+H)^n(G^{}𝒪(H))`$
which translates into the formula given in the statement. ∎

### 2.6.

Therefore, up to the bookkeeping of inclusion-exclusion and to trivial algebraic manipulations, the problem of computing $`i_{}c_{\text{SM}}(S)`$ is reduced by Theorem 2.1 to the computation of the shadow $`G`$ of the graph $`\mathrm{\Gamma }`$ of a rational map. This is the key ingredient, and since it yields more generally the Segre class of any closed subscheme of $`^n`$ we discuss it separately, in §3.

Summarizing: given the ideal $`I=(F_1,\mathrm{},F_r)`$ of $`S`$, an algorithm computing $`i_{}c_{\text{SM}}(S)`$ will

* list all products $`F=_{i_1<\mathrm{}<i_s}F_{i_1}\mathrm{}F_{i_s}`$;
* for each such $`F`$, compute the jacobian ideal $`J=(\frac{F}{z_0},\mathrm{},\frac{F}{z_n})`$, and apply the procedure described in §3 in order to compute the corresponding class $`G`$;
* apply Theorem 2.1 to this class, and obtain $`i_{}c_{\text{SM}}(X)`$ for the hypersurface $`X`$ corresponding to $`F`$;
* apply inclusion-exclusion to reconstruct $`i_{}c_{\text{SM}}(S)`$.

The coefficient of $`H^n`$ in $`i_{}c_{\text{SM}}(S)`$ gives the Euler characteristic of the support of $`S`$.

### 2.7.

If $`r`$ is the number of generators of the ideal of $`S`$, one ‘shadow’ computation is required for each of the $`2^r1`$ hypersurfaces invoked by inclusion-exclusion. This causes an exponential slow-down of the procedure as the codimension of $`S`$ increases.

It is somewhat amusing that the result of the computation, that is, $`i_{}c_{\text{SM}}(S)`$, only depends on the support of $`S`$, even if in no place does the algorithm explicitly compute the support of $`S`$, or of the hypersurfaces $`X`$ considered at intermediate stages. In fact, introducing intermediate computations of supports may speed up the algorithm: any procedure ‘simplifying’ the input $`I`$—in the sense of reducing the number and degree of the generators, without altering the radical of $`I`$—should lead to an increase in the efficiency of the procedure.

### 2.8.

The procedure is easily adapted to the computation of the Euler characteristic of (the support of) a closed subscheme $`S`$ of affine space $`𝔸^n`$, given its defining ideal. This can be done in several ways: for example, one may homogenize the ideal of $`S`$, obtaining the closure $`\overline{S}^n`$; then multiply this ideal by the equation of the hyperplane $`L`$ at infinity, obtaining the union $`\overline{S}L^n`$; and then compute

$$\chi (S)=\chi (\overline{S}L)(n+1).$$

As an alternative, one may intersect with the hyperplane at infinity, obtaining a ‘limit’ subscheme $`\underset{¯}{S}^{n1}`$; and then

$$\chi (S)=\chi (\overline{S})\chi (\underset{¯}{S}).$$

This approach appears to be much faster in practice.

## 3. Computing Segre classes of subschemes of $`^n`$

### 3.1.

We can now lift the restriction on the characteristic of the ground field $`k`$, as they are irrelevant for the considerations in this section. Again we let $`i:S^n`$ be a closed embedding of a scheme $`S`$ in projective space $`^n=^nk`$; our goal is to give an explicit procedure computing the push-forward

$$i_{}s(S,^n)A_{}^n$$

of the Segre class $`s(S,^n)`$ of $`S`$ in $`^n`$. By Proposition 3.1 this will be reduced to the computation of a ‘shadow’, as has been the case in §2; we will then discuss the computation of shadows, in §3.5 and ff.

### 3.2.

Let $`I=(f_0,\mathrm{},f_N)k[z_0,\mathrm{},z_n]`$ be a homogeneous ideal defining $`S`$. We may and will assume that the generators $`f_i`$ are all of the same degree $`r`$; in other words, we write $`S`$ as the zero-scheme of a section of $`𝒪(rH)^{(n+1)}`$:

$$(f_0,\mathrm{},f_N):𝒪_^n𝒪(rH)^{(n+1)}.$$

Projectivizing, we get a rational map

$$^n^N$$

and we let

$$\mathrm{\Gamma }_I^n\times ^N$$

denote the (closure of the) graph of this map. Denote by $`K`$ the pull-back of the hyperplane class from the $`^N`$ factor, and by $`\pi `$ the projection $`\mathrm{\Gamma }_I^n`$. The shadow of $`\mathrm{\Gamma }_I`$ is the class

$$G=g_0+g_1H+\mathrm{}+g_nH^nA_{}^n,$$

where $`g_i`$ is the degree of $`\pi _{}(K^i[\mathrm{\Gamma }_i])`$.

### 3.3.

Now we can state and prove the simple result used in the proof of Theorem 2.1. The statement, as that proof, uses the notations from \[Alu99\].

###### Proposition 3.1.

With the above positions,

$$i_{}s(S,^n)=1c(𝒪(rH))^1\left(G𝒪(rH)\right).$$

###### Proof.

By construction, the graph $`\mathrm{\Gamma }_I`$ is isomorphic to the blow-up of $`^n`$ along $`S`$, and the class of the exceptional divisor $`E`$ on $`\mathrm{\Gamma }_I`$ equals the restriction of $`c_1(𝒪(1))`$ from $`(𝒪(rH)^{(n+1)})^n`$. Chasing this identification, we see that the class of $`E`$ is $`rHK`$. Hence using \[Ful84\], Corollary 4.2.2:

$$s(S,^n)=\pi _{}\frac{[E]}{1+E}=\pi _{}\frac{[rHK]}{1+rHK}.$$

Pushing forward to $`^n`$, this can be manipulated as follows:

$`\pi _{}{\displaystyle \frac{[rHK]}{1+rHK}}`$ $`=\pi _{}\left([\mathrm{\Gamma }_I]{\displaystyle \frac{1}{1+rHK}}[\mathrm{\Gamma }_I]\right)`$
$`=1\pi _{}\left({\displaystyle \frac{1}{1+rH}}{\displaystyle \frac{1+rH}{1+rHK}}[\mathrm{\Gamma }_I]\right)`$
$`=1c(𝒪(rH))^1\pi _{}\left(\left({\displaystyle \frac{1}{1K}}[\mathrm{\Gamma }_I]\right)𝒪(rH)\right)`$
$`=1c(𝒪(rH))^1\left(G𝒪(rH)\right)`$
as claimed. ∎

### 3.4.

The upshot of Theorem 2.1 and Proposition 3.1 is that we can compute Chern-Schwartz-MacPherson classes and Segre classes (and hence Fulton classes) if we can extract the integers $`g_i`$ giving the coefficients of the class $`G`$ determined by a graph $`\mathrm{\Gamma }_I`$. That is, we must be able to

* obtain $`\mathrm{\Gamma }_I`$ explicitly;
* intersect $`\mathrm{\Gamma }_I`$ with general hyperplanes;
* project the intersections down to $`^n`$;

and compute the degree of these projections.

Each of these steps is easily implemented in any of the standard symbolic computations packages; we briefly discuss this in the following subsections.

### 3.5. Obtaining $`\mathrm{\Gamma }_I`$ explicitly

A bihomogeneous ideal for the graph $`\mathrm{\Gamma }_I`$ can be given in the ring

$$k[t_0,\mathrm{},t_N,z_0,\mathrm{},z_n]$$

by the following trick (going back at least as far as \[Mic64\], proof of Lemma 1): adjoin an auxiliary variable $`u`$ to the ring, and consider the ideal

$$J=(t_0uf_0,\mathrm{},t_Nuf_N)$$

in the extended ring. Then the ideal for $`\mathrm{\Gamma }_I`$ is the contraction

$$J_0:=Jk[t_0,\mathrm{},t_N,z_0,\mathrm{},z_n].$$

Indeed, $`J`$ is the kernel of the homomorphism

$$k[u,t_0,\mathrm{},t_N,z_0,\mathrm{},z_n]k[u,z_0,\mathrm{},z_n]$$

obtained by mapping $`t_i`$ to $`uf_i`$; a polynomial $`Pk[t_0,\mathrm{},t_N,z_0,\mathrm{},z_n]`$ maps to $`0`$ by this map if and only if $`P`$ vanishes whenever $`(t_0:\mathrm{}:t_N)=(f_0:\mathrm{}:f_N)`$.

The ideal $`J_0`$ of $`\mathrm{\Gamma }_I`$ can thus be obtained by standard elimination theory: choose a monomial order so that $`u`$ precedes the other variables; compute a Gröbner basis for $`J`$; and eliminate $`u`$ to obtain the intersection of $`J`$ with the ring $`k[t_0,\mathrm{},t_N,z_0,\mathrm{},z_n]`$.

Needless to say, this operation is rather computationally expensive. Of course, any other algorithm computing the Rees algebra of $`I`$ can be employed here; the topic is treated extensively in \[Vas98\], §7.2.

### 3.6. Intersecting $`\mathrm{\Gamma }_I`$ with general hyperplanes

Programs such as Macaulay2 include the option of producing ‘random’ elements of given degree in a ring; for $`i=1,\mathrm{},n`$ we can inductively set

$$J_i:=\text{saturate}(J_{i1}+(\mathrm{}_i),(t_0,\mathrm{},t_N)),$$

where $`\mathrm{}_i=\mathrm{}_i(t_0,\mathrm{},t_N)`$ is a random linear polynomial in $`k[t_0,\mathrm{},t_N]`$, and the saturation is necessary to remove possible components in the intersection supported on the irrelevant ideal, see below.

Of course we have to take care that random is sufficiently random. For the purposes of this computation, a hyperplane is general if it does not contain any component of the object it is intersecting, that is, if it is not contained in any of the associated primes of the corresponding ideal. This can be explicitly checked, for example by making sure that the dimension decreases upon intersecting with the hyperplane. Thus the ideals $`J_i`$ can be obtained as above, by producing enough random $`\mathrm{}_i`$ until a general one is found.

As for the saturation, the manipulation of the ideals in $`k[t_0,\mathrm{},t_N,z_0,\mathrm{},z_n]`$ amounts to working in $`𝔸^{n+1}\times 𝔸^{N+1}`$. Saturating with respect to the irrelevant ideal $`(t_0,\mathrm{},t_N)`$ guarantees that there is a bijection between the components of the subscheme defined by $`J_i`$ in $`𝔸^{n+1}\times 𝔸^{N+1}`$ and those (about which we are interested) in $`𝔸^{n+1}\times ^N`$.

###### Example 3.2.

Here is an example showing that extra components may indeed appear. Consider $`I=(z_0,z_1)`$ in $`k[z_0,z_1]`$. Then, with notations as above,

$$J_0=(z_0t_1z_1t_0).$$

Intersecting by $`t_0`$ does decrease the dimension (so that $`t_0`$ is general in the above sense), but creates a component supported on the irrelevant ideal:

$$(z_0t_1z_1t_0)+(t_0)=(t_0,t_1)(z_0,t_0).$$

Saturating with respect to $`(t_0,t_1)`$ eliminates such spurious components.

### 3.7. Projecting down to $`^n`$

This is also done by elimination theory. Once $`J_i`$ is obtained, we can ask for the Gröbner basis with respect to a monomial ordering in which $`t_0,\mathrm{},t_N`$ precede $`z_0,\mathrm{},z_n`$, then eliminate $`t_0,\mathrm{},t_N`$. This computes

$$J_ik[z_0,\mathrm{},z_n],$$

that is, the homogeneous ideal in $`^n`$ of the projection of the $`i`$-th linear section.

### 3.8.

Programs such as Macaulay2 compute the degree of the scheme defined by a given homogeneous ideal without difficulty. Applying this to the ideal obtained in the previous step produces the list of integers

$$g_0=1,g_1,\mathrm{},g_n$$

needed in Theorem 2.1 and Proposition 3.1.

### 3.9.

Every scheme $`S`$ embeddable in a nonsingular variety $`M`$ has an intrinsic Fulton class

$$c_\text{F}(S)=c(TM)s(S,M)$$

(see \[Ful84\], Example 4.2.6(a)). As $`i_{}s(S,^n)`$ is available via the procedure described above, so is

$$i_{}c_\text{F}(S)=(1+H)^{n+1}i_{}s(S,^n)$$

for a projective scheme.

That $`c_\text{F}(S)`$ is intrinsic means that it does not depend on the chosen embedding. For example, if $`S`$ itself is nonsingular, then

$$c_\text{F}(S)=c(TS)[S],$$

and in particular

$$i_{}c_\text{F}(S)=c(TS)[S]=\chi (S)$$

computes (in characteristic 0) the Euler characteristic of $`S`$. It seems, however, that the computation of the Euler characteristic via $`h^{ij}`$ would be much faster in this case.

Not much is known about $`c_\text{F}(S)`$ in general, even regarding $`c_\text{F}(S)`$ (cf. \[Ful84\], Example 4.2.6(b)). If $`S`$ is a local complete intersection, then $`c_\text{F}(S)`$ equals the class of the virtual tangent bundle of $`S`$. In this case, identifying the difference between $`c_\text{F}(S)`$ and the functorial $`c_{\text{SM}}(S)`$ has been identified by Yokura as a Verdier-type Riemann-Roch problem; cf. Example refmilnor.

## 4. Examples

We won’t reproduce here the Macaulay2 code implementing the above steps, as further details seem unnecessary, and our code is certainly much less than optimal. A documented copy of the code (and of future improvements) is available at

http://www.math.fsu.edu/~aluffi/CSM/CSM.html

In the present version, loading the code (named CSM.m2) produces several functions:

* segre
* cf
* csm
* euleraffine

with hopefully evident meaning. The first three items accept a homogeneous ideal in a polynomial ring as argument; euleraffine accepts a (not necessarily homogeneous) ideal in a polynomial ring.

The simple examples which follow are meant to illustrate the use of these functions.

```
Macaulay 2, version 0.9
--Copyright 1993-2001, D. R. Grayson and M. E. Stillman
--Singular-Factory 1.3b, copyright 1993-2001, G.-M. Greuel, et al.
--Singular-Libfac 0.3.2, copyright 1996-2001, M. Messollen

i1 : load "CSM.m2"
--loaded CSM.m2

```

Most of the examples are chosen in projective spaces of dimension 2,3, and 4 over $``$:

```
i2 : ringP2=QQ[x,y,z]; ringP3=QQ[x,y,z,w]; ringP4=QQ[x,y,z,w,t];

```

###### Example 4.1 (Three concurrent lines in $`^3`$).

The Segre class of the reduced scheme $`S`$ supported on three general distinct lines through a point in $`^3`$ is computed by

```
i5 : use ringP3; segre ideal(x*y,x*z,y*z)
                   3     2
Segre class : - 10H  + 3H

```

The output is written in the Chow ring of $`^3`$, where $`H`$ denotes the hyperplane class; thus the result is

$$i_{}s(S,^3)=3[^1]10[^0].$$

The class changes if the lines become coplanar. For instance, consider the ideal $`(z,xy(x+y))`$ (in order to compute the Segre class in this case, the routine modifies the ideal so that all generators have the same degree:

$$(x^2z,y^2z,z^3,z^2w,xy(x+y));$$

this ideal defines the same scheme, so it yields the same Segre class).

```
i7 : segre ideal(z,x*y*(x+y))
                   3     2
Segre class : - 12H  + 3H

```

Or we may argue that since three coplanar lines form a plane curve of degree 3, the Fulton class of $`S`$ must equal the class for a nonsingular plane cubic; then use that Fulton classes are intrinsic (see §3.9) to compute the Segre class in $`^3`$. This gives the same result:

$$\frac{3H^2}{(1+H)^4}=3H^212H^3.$$

In order to compute directly the Fulton classes for these two examples:

```
i8 : CF ideal(x*y,x*z,y*z)
                 3     2
Fulton class : 2H  + 3H

i9 : CF ideal(z,x*y*(x+y))
                 2
Fulton class : 3H

```

while the Chern-Schwartz-MacPherson classes are:

```
i10 : CSM ideal(x*y,x*z,y*z)
                                    3     2
Chern-Schwartz-MacPherson class : 4H  + 3H

i11 : CSM ideal(z,x*y*(x+y))
                                    3     2
Chern-Schwartz-MacPherson class : 4H  + 3H

```

This example illustrates that Chern-Schwartz-MacPherson classes are, to some extent, ‘combinatorial objects’: unlike Fulton classes, they do not tell the difference between the two configurations.

###### Example 4.2 (plane cubics).

However, Fulton classes cannot tell the difference between a nonsingular plane cubic and a singular one. We switch to dimension 2, which speeds up the computations somewhat; the Fulton classes for $`(x^3+y^3+z^3)`$ and $`(xy(x+y))`$ agree:

```
i12 : use ringP2; CF ideal(x^3+y^3+z^3); CF ideal(x*y*(x+y))
Fulton class : 3H
Fulton class : 3H

```

while the Chern-Schwartz-MacPherson classes for the same ideals differ:

```
i15 : CSM ideal(x^3+y^3+z^3); CSM ideal(x*y*(x+y))
Chern-Schwartz-MacPherson class : 3H
                                    2
Chern-Schwartz-MacPherson class : 4H  + 3H

```

The Euler characteristic in the second case is computed to be $`4`$, as it should. Taking the ideal $`(xy(x+y)))`$ in the affine plane gives a cone, so the Euler characteristic of the corresponding scheme in $`𝔸^2`$ must be $`1`$:

```
i17 : use QQ[x,y]; euleraffine ideal(x*y*(x+y))

o18 = 1

```

while the Euler characteristic of the nonsingular affine cubic $`x^3+y^3=1`$ is $`3`$:

```
i19 : euleraffine ideal(x^3+y^3-1)

o19 = -3

```

###### Example 4.3 (A nonreduced example).

Here are $`c_\text{F}`$ and $`c_{\text{SM}}`$ for a reduced pair of lines in $`^2`$:

```
i20 : use ringP2; CF ideal(x*y); CSM ideal(x*y)
                 2
Fulton class : 2H  + 2H
                                    2
Chern-Schwartz-MacPherson class : 3H  + 2H

```

In $`^3`$, we can consider the ideal $`(xy,xz,yz,z^2)=(x,z)(y,z)`$: this defines a scheme supported on two concurrent lines, but with a nilpotent on the point of intersection. This can be checked with Macaulay2:

```
i23 : use ringP3; ass ideal(x*y,x*z,y*z,z^2)

o24 = {ideal (z, x), ideal (z, y), ideal (z, y, x)}

o24 : List

```

And here are $`c_\text{F}`$ and $`c_{\text{SM}}`$:

```
i25 : CF ideal(x*y,x*z,y*z,z^2); CSM ideal(x*y,x*z,y*z,z^2)
                 3     2
Fulton class : 4H  + 2H
                                    3     2
Chern-Schwartz-MacPherson class : 3H  + 2H

```

As should be expected, $`c_\text{F}`$ detects the embedded component, while $`c_{\text{SM}}`$ ignores it.

###### Example 4.4 (Quintic threefold).

Fulton and Chern-Schwartz-MacPherson classes agree for nonsingular varieties $`S`$, as they both give the total (homology) Chern class of the tangent bundle of $`S`$. Here is the computation for the Fermat quintic in $`^4`$:

```
i27 : use ringP4; quintic=ideal(x^5+y^5+z^5+w^5+t^5);

o28 : Ideal of ringP4

i29 : CF quintic; CSM quintic
                     4      3
Fulton class : - 200H  + 50H  + 5H
                                        4      3
Chern-Schwartz-MacPherson class : - 200H  + 50H  + 5H

```

giving Euler characteristic$`=200`$, as it should be. Computing the Euler characteristic of singular quintic threefolds is equally straightforward; here is a random example inspired by reading about elliptic Calabi-Yau threefolds:

```
i31 : CSM ideal(x^3*t^2+x*z^4+w^5-y^2*t^3)
                                    4      3
Chern-Schwartz-MacPherson class : 4H  + 38H  + 5H

```

that is, the hypersurface obtained by closing up $`y^2=x^3+z^4x+w^5`$ in $`^4`$ has Euler characteristic 4.

###### Example 4.5 (Discriminants).

Identify $`^3`$ with the space of triples of points in $`^1`$. The set of nonreduced triples forms a hypersurface of degree $`4`$. Here is its Chern-Schwartz-MacPherson class:

```
i32 : use ringP3;

i33 : CSM ideal(-27*x^2*w^2+18*x*w*y*z+y^2*z^2-4*y^3*w-4*x*z^3)
                                    3     2
Chern-Schwartz-MacPherson class : 4H  + 6H  + 4H

```

This agrees with the computation in \[Alu98\]. In general, the Euler characteristic of the discriminant hypersurface for $`d`$-tuples is $`(d+1)`$.

Identifying $`^5`$ with the space of plane conics, we have similarly a discriminant hypersurface parametrizing singular conics, that is, pairs of lines; explicitly, this can be realized as the determinant of a symmetric $`3\times 3`$ matrix. Its Chern-Schwartz-MacPherson class:

```
i34 : use QQ[x,y,z,w,t,u];

i35 : CSM ideal det matrix {{x,y,z},{y,w,t},{z,t,u}}
                                    5      4      3     2
Chern-Schwartz-MacPherson class : 6H  + 12H  + 14H  + 9H  + 3H

```

The Chern-Schwartz-MacPherson class of the discriminant of plane cubics is computed in \[Alu98\], Corollary 12; but that computation seems to be computationally out of reach of CSM.m2 at present.

###### Example 4.6 ($`d`$-tuples).

A good source of examples of applications of Segre classes is enumerative geometry. As the procedure described in §3 computes the Segre class precisely by solving a number of enumerative problems, it is hardly surprising that the enumerative answers can be decoded back from the Segre class; the examples that follow illustrate this procedure.

The degree of the PGL(2)-orbit closure of a configuration of $`d`$ points in $`^1`$ (counting multiplicities) has been studied in \[AF93\]. For a configuration $`C`$, this degree computes the number (with multiplicities) of translates of $`C`$ which contain three given general points; the ‘predegree’ of an orbit closure counts such translates according to automorphisms of the $`d`$-tuple. In order to use a Segre class to compute this predegree, one can parametrize translates of a fixed $`C`$ by the $`^3`$ of $`2\times 2`$ matrices

$$\left(\begin{array}{cc}x& y\\ z& w\end{array}\right);$$

the condition that the translate of $`C`$ contains a point determines a surface in this $`^3`$, and the predegree is given by the number of points of intersection of three general such surfaces. The problem of computing this number is not immediately reduced to Bézout’s theorem because these surfaces have an excess intersection. In general, contributions of excess intersections can be evaluated in terms of a Segre class by using Proposition 9.1.1 in \[Ful84\]. With this in mind, the predegree of the orbit closure is given by

$$d^3(1+dH)^3i_{}s(S,^3),$$

where $`d`$ is the degree of $`C`$, and $`S`$ is the base scheme of the map $`^3^d`$ mapping a matrix as above to the corresponding translate of $`C`$.

For a concrete example, consider the $`5`$-tuple with ideal generated by

$$s(s+3t)^2(s+5t)(s+16t)$$

in $`^1`$. The reader should have no difficulties obtaining the ideal of $`S`$. Using this, our routine computes $`i_{}s(S,^3)`$ as

$$\{\begin{array}{cc}\hfill 13H^270H^3& \\ \hfill 11H^258H^3& \\ \hfill 9H^234H^3& \\ \hfill 7H^222H^3\end{array}$$

in characteristic $`2`$, $`3`$, $`5`$, and $`7`$ respectively. For example (the ideal is loaded from a separate file):

```
i36 : use ZZ/3[x,y,z,w]; load "dtupleideal.m2";
--loaded dtupleideal.m2

i38 : segre dtupleideal
                   3      2
Segre class : - 58H  + 11H

```

Using the formula given above, these classes correspond to predegrees $`0`$, $`18`$, $`24`$, $`42`$ respectively in char. $`2`$, $`3`$, $`5`$, $`7`$. These numbers are nicely explained by the result in \[AF93\]: in characteristic $`2`$ the tuple collapses to a pair of points, hence its orbit closure has dimension 2; in characteristic $`3`$ it consists of three points with multiplicities $`3,1,1`$; in characteristic $`5`$, three points with multiplicities $`2,2,1`$; and in characteristic $`7`$ (and most others, including 0) of four points, one of which double. These multiplicities determine the predegree of the orbit closure, by \[AF93\], Proposition 1.3; applying that result gives the same predegrees as obtained here by brute force.

###### Example 4.7 (Milnor classes).

The function milnor computes both Fulton and Chern-Schwartz-MacPherson classes, giving $`i_{}`$ of the difference

$$c_{\text{SM}}(S)c_\text{F}(S).$$

This class (up to a sign, cf. the definition of $`(Z)`$ in \[PP01\], p. 64) has been named the Milnor class of $`S`$; to our knowledge, it has not been studied in any depth for schemes other than reduced local complete intersection.

If $`S`$ is a hypersurface with isolated singularities, then $`i_{}`$ of the Milnor class of $`S`$ is simply (up to sign) $`\mu H^n`$, where $`\mu `$ is the sum of the Milnor numbers of the singularities; this is the reason for the choice of terminology.

```
i39 : use ringP2; milnor ideal(y^6+z*x^3*y^2+z^2*x^4)
                    2
Fulton class : - 18H  + 6H
Chern-Schwartz-MacPherson class : 6H
                  2
Milnor class : 18H

```

This says that the sum of the Milnor numbers of the curve $`y^6+x^3y^2z+x^4z^2=0`$ in $`^2`$ is 18. It may be checked that this curve has singularities at $`(x:y:z)=(1:0:0)`$ and $`(0:0:1)`$, with Milnor numbers respectively $`3`$ and $`15`$, consistently with this information.

More generally, the coefficient of $`H^n`$ in the output of milnor for an arbitrary hypersurface of $`^n`$ computes Adam Parusiński’s generalization of the Milnor number, \[Par88\], whether the singularities are isolated or not.

Our routine compute a notion of Milnor class for arbitrary projective schemes. For example, the following would be the computation of the Milnor class of the union of a line and a plane in $`^3`$:

```
i41 : use ringP3; milnor ideal(x*y,x*z)
                 3     2
Fulton class : 2H  + 4H  + H
                                    3     2
Chern-Schwartz-MacPherson class : 4H  + 4H  + H
                 3
Milnor class : 2H

```

In fact such computations may be performed in any characteristic; so far as we know, no interpretation of the class is known in positive characteristic.

Recent work of Jörg Schürmann, \[Sch\], relates Milnor classes of complex local complete intersection with his generalization of Deligne’s functor of vanishing cycles.


format: text

text:
# Nonequilibrium generalization of Förster-Dexter theory for excitation energy transfer*footnote **footnote *published in Chemical Physics, 275, pp. 319–332 (2002)

## I Introduction

Excitation energy transfer (EET) is ubiquitous in photo sensitive materials and is one of the key steps in photosynthesis. Since the seminal works of Förster and Dexter (FD), their rate expressions have been confirmed by numerous experiments and have played fundamental roles in understanding various luminescence phenomena. In these advances, the spectral overlap expression of Förster, which allows identification of the reaction rate without any resort to a model Hamiltonian, has been essential.

The rate expressions of FD are applications of the Fermi’s golden rule (FGR), which rely on the smallness of the resonance interactions. The spectral overlap expression of Förster derives from the additional simplification that bath modes coupled to the energy donor and acceptor are independent of each other. If there are common bath modes, such a simple expression is not in general valid. However, within the harmonic oscillator bath model, rigorous extensions of the FD theory can be made with the use of small polaron transformation, and can be further generalized for the study of long-time dynamics based on the Redfield-type equation and for the understanding of exciton transport in molecular crystals. In recent years, theoretical advances to cope with new experiments have been made, such as microscopic consideration of the medium effect, generalization of the FD rate expression for disordered multichromorphic systems, and unified theories covering up to the intermediate and strong coupling regimes.

Although often not noticed, the assumption of stationarity is implicit in the FD theory. The FGR is valid only when the initial density operator commutes with the zeroth order Hamiltonian and the bath time scale is much shorter than that of the electronic transition. For EET processes occurring in nanosecond or longer time scale, one may safely assume that the bath modes have already relaxed and become equilibrated with the excited donor before the energy transfer takes place, unless there are ultra-slow modes or spin interactions with comparable time scales. Application of the FGR, thus the FD theory, can be justified for this case. However, EET in general is a nonstationary process where nonequilibrium relaxation of the nuclear degrees of freedom occurs during and after the electronic excitation. For fast EET processes occurring in a time scale comparable to the bath relaxation time, the reaction kinetics predicted by the FD theory may not be accurate enough.

The importance of the nonequilibrium effects for fast EET was in fact recognized long time ago, and was named as hot transfer. Due to experimental limitations, however, the earlier experiments and relevant theories were concerned with the frequency domain situation where the reaction rate at issue is the stationary long time limit in the presence of an excitation field tuned for the hot transfer. Time dependent pump-probe situation was considered later by Sumi, who formulated a time dependent generalization of the FD theory based on a nonequilibrium golden rule approximation.

With the advance of ultrafast spectroscopy, it has become possible to induce the electronic excitation in the femtosecond scale. Experiments performed in this manner reveal systems where the EET rate is comparable to the vibrational relaxation rate of some modes. A typical example for this is the EET from B800 to B850 in the light harvesting complex 2 (LH2), which is known to occur in about $`1\mathrm{ps}`$. Evidences for fast EET were found in other systems also such as the conjugated polymer, dendrimers, and the photosynthetic reaction center. In general, the microscopic mechanisms of the EET in these systems are quite complicated, and considerations of multipolar transitions, multichromorphic effects, and disorder may be important. However, simple comparison of time scales indicates that examination of the nonequilibrium effects cannot be overlooked. The theory of Sumi and recent theories on intermediate and strong coupling seem suitable for these considerations. However, the nature of the approximation involved in the bath relaxation dynamics, upon which the nonequilibrium kinetics is sensitive, is not clear in these approaches.

In the present work, we provide a straightforward and rigorous nonequilibrium generalization of the FD theory. The procedure is to go through the same perturbation theory as in deriving the FGR, but starting from the nonstationary initial states and considering full time dependences. Our analysis is limited to the usual perturbation regime of the FD theory. We assume that the resonance interaction is small enough to validate second order perturbation theory and that the reaction is virtually irreversible due to either energetic or entropic reason. However, the excitation bath coupling is treated rigorously. The present theory is analogous to the nonequilibrium generalization of the electron transfer, but an important distinction is that we provide a spectral overlap expression valid for arbitrary bath without common modes, a typical situation for the EET.

Our theory can be considered as the pump-probe version of the hot transfer rate theories. More importantly, our spectral overlap expression brings a connection between the time dependent reaction rate and the modern ultrafast spectroscopy experiment, which allows direct determination of the reaction rate or enables experimental confirmation whether the usual assumption of the EET kinetics is valid. In addition, we provide calculations of the time dependent rate for the model of the harmonic oscillator bath, which illustrate some features of the nonequilibrium EET kinetics.

The sections are organized as follows. In Sec. IIA, we present the main formalism and provide the spectral overlap expression valid for general bath Hamiltonian without common modes. Section IIB provides a complementary result of an explicit rate expression for the harmonic oscillator bath. In Sec. III, model calculations are made. Sec. IV concludes with summaries and the relevance of the present theory with recent experiments.

## II Theory

### A General bath without common modes

The system consists of two distinctive chromophores, donor ($`D`$) and acceptor ($`A`$). The state where both $`D`$ and $`A`$ are in their ground electronic states is denoted as $`|g`$. The state where $`D`$ is excited while $`A`$ remains in the ground state is denoted as $`|D=a__D^{}|g`$, where $`a__D^{}`$ is the corresponding creation operator, and $`|A=a__A^{}|g`$ is defined similarly. We assume that both chromophores are excited to singlet states and do not consider multiexciton states. Therefore, the three electronic states $`|g`$, $`|D`$, and $`|A`$ form a complete set of electronic states. All the rest of the dynamic degrees of freedom such as molecular vibrations and solvation coordinates are included in the bath. The bath Hamiltonian is defined as that in the ground state $`|g`$ and is assumed to be $`H_b=H_{b_D}+H_{b_A}`$, where the subscripts of $`D`$ and $`A`$ denote the components coupled to chromophores $`D`$ and $`A`$, respectively. That is, in the present work, the effect of common modes is disregarded. For EET processes in a medium where phonons and vibrations are localized, this assumption seems reasonable.

Since we consider the excitation dynamics during a time much shorter than the lifetime of the excited state, we neglect the spontaneous decay channels of the excited states. Adopting a second quantization notation where $`|g`$ is treated as if the vacuum state, the zeroth order Hamiltonian describing the interaction-free dynamics can be written as

$$H_0=ϵ__Da__D^{}a__D+ϵ__Aa__A^{}a__A+H_b\text{ }\text{,}$$
(1)
where $`ϵ__D`$ and $`ϵ__A`$ are excitation energies of $`D`$ and $`A`$.

The resonance interaction between $`|D`$ and $`|A`$ is represented by

$$H_{DA}=J(a__D^{}a__A+a__A^{}a__D)\text{ }\text{,}$$
(2)
where $`J`$ is a function of the position vectors and the transition dipoles of $`D`$ and $`A`$. The functional form of $`J`$ depends on the mechanism of EET. For dipole-dipole interaction, it varies as the inverse third power of the distance between $`D`$ and $`A`$. For exchange interaction, it is an exponential function of the distance. Here we do not specify the detailed mechanism, but simply assume that it is small enough to warrant a perturbation analysis and does not have any dependence on the bath operators (vibrational degrees of freedom), so called Condon approximation.

The excitation bath coupling is assumed to be as follows:

$$H_{eb}=B__Da__D^{}a__D+B__Aa__A^{}a__A\text{ }\text{,}$$
(3)
where $`B__D`$ and $`B__A`$ are bath operators coupled to $`|D`$ and $`|A`$ respectively. These operators and the bath Hamiltonian can be arbitrary except for the following condition:

$$[H_{b_D},H_{b_A}]=[H_{b_D},B__A]=[H_{b_A},B__D]=0\text{ }\text{,}$$
(4)
which implies that the bath modes coupled to $`|D`$ and $`|A`$ are independent of each other. This assumption can be justified if the chromophores $`D`$ and $`A`$ are far enough apart from each other and the major nuclear modes coupled to excitations are localized to either $`D`$ or $`A`$, which can be consistent with the assumption of smallness of $`J`$.

Summing up Eqs. (1)-(3), the total Hamiltonian describing the dynamics of the chromophores, in the single excitation manifold, and the bath is given by

$$H=H_0+H_{DA}+H_{eb}\text{ }\text{.}$$
(5)
For $`t<0`$, the chromophores are assumed to be in the state $`|g`$ and thus the total Hamiltonian is equal to $`H_b`$. The bath is assumed to be in the canonical equilibrium of $`H_b`$ during this period. At time zero, an impulsive pulse selectively excites $`D`$. Here we approximate this as a delta pulse in time. Then, the density operator at time zero, right after the irradiation, is given by

$$\rho (0)=|DD|e^{\beta H_b}/Z_b\text{ }\text{,}$$
(6)
where $`\beta =1/k__BT`$ and $`Z_b=Tr_b\{e^{\beta H_b}\}`$.

The probability at time $`t`$ for the excitation to be found at $`A`$ is given by

$$P_A(t)=Tr_b\left\{A|e^{iHt/\mathrm{}}\rho (0)e^{iHt/\mathrm{}}|A\right\}\text{ }\text{.}$$
(7)
For short enough time compared to $`\mathrm{}/J`$, a perturbation expansion of this with respect to $`H_{DA}`$ can be made. Inserting the first order approximation of the time evolution operator $`e^{iHt/\mathrm{}}`$ and the complex conjugate into Eq. (7), we obtain the following expression valid up to the second order of $`J`$:

$`P_A(t)`$ $``$ $`{\displaystyle \frac{J^2}{\mathrm{}^2}}{\displaystyle _0^t}𝑑t^{}{\displaystyle _0^t}𝑑t^{\prime \prime }e^{i(ϵ_Aϵ_D)(t^{}t^{\prime \prime })/\mathrm{}}`$ (10)
$`\times {\displaystyle \frac{1}{Z_b}}Tr_b\{e^{i(H_b+B__A)(t^{}t^{\prime \prime })/\mathrm{}}e^{i(H_b+B__D)t^{}/\mathrm{}}`$
$`\times e^{\beta H_b}e^{i(H_b+B__D)t^{\prime \prime }/\mathrm{}}\}\text{ }\text{.}`$
The time dependent EET rate is then defined as the derivative of this acceptor probability as follows:

$`k(t)`$ $``$ $`{\displaystyle \frac{d}{dt}}P_A(t)`$ (11)
$``$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(ϵ__Dϵ__A)t^{}/\mathrm{}}{\displaystyle \frac{1}{Z_b}}Tr_b\{e^{i(H_b+B__D)t/\mathrm{}}`$ (13)
$`\times e^{i(H_b+B__A)t^{}/\mathrm{}}e^{i(H_b+B__D)(tt^{})}e^{\beta H_b}\}]\text{ }\text{.}`$
Under the assumption of Eq. (4), the trace over the bath degrees of freedom comprising $`H_{b_D}`$ and $`H_{b_A}`$ can be decoupled from each other in the following way:

$`k(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(ϵ__Dϵ__A)t^{}/\mathrm{}}`$ (18)
$`\times {\displaystyle \frac{1}{Z_{b_A}}}Tr_{b_A}\left\{e^{iH_{b_A}t^{}/\mathrm{}}e^{i(H_{b_A}+B__A)t^{}/\mathrm{}}e^{\beta H_{b_A}}\right\}`$
$`\times {\displaystyle \frac{1}{Z_{b_D}}}Tr_{b_D}\{e^{i(H_{b_D}+B__D)t/\mathrm{}}e^{iH_{b_D}t^{}/\mathrm{}}`$
$`\times e^{i(H_{b_D}+B__D)(tt^{})/\mathrm{}}e^{\beta H_{b_D}}\}]\text{ }\text{,}`$
where $`Z_{b_A}=Tr_{b_A}\{e^{\beta H_{b_A}}\}`$ and $`Z_{b_D}=Tr_{b_D}\{e^{\beta H_{b_D}}\}`$. Equation (18) is the nonequilibrium generalization of the FD rate, but expressed in the time domain. As has been outlined in the introduction, this result has been obtained by applying second order perturbation theory to the time dependent density operator with the nonstationary initial condition of Eq. (6). The decoupled form of Eq. (18) makes it possible to express the reaction rate as an overlap of frequency domain spectral profiles of independent donor and acceptor, as will be shown later. Before going through this procedure, it is meaningful to clarify the difference between the present result and the FD rate expression. Two additional approximations are necessary.

The first is the assumption of stationarity, equivalent to the following replacement:

$`e^{i(H_{b_D}+B__D)(tt^{})/\mathrm{}}e^{\beta H_{b_D}}e^{i(H_{b_D}+B__D)(tt^{})/\mathrm{}}`$ (19)
$`{\displaystyle \frac{Z_{b_D}}{Z_{b_D}^{}}}e^{\beta (H_{b_D}+B__D)}\text{ }\text{,}`$ (20)
where $`Z_{b_D}^{}=Tr_{b_D}\{e^{\beta (H_{b_D}+B__D)}\}`$. This approximation implies that the nuclear dynamics on the excited donor potential energy surface is ergodic in a time scale shorter than that of the EET transfer kinetics. We define the reaction rate based on this fully relaxed density operator as

$`k_r(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(ϵ__Dϵ__A)t^{}/\mathrm{}}`$ (24)
$`\times {\displaystyle \frac{1}{Z_{bA}}}Tr_{bA}\left\{e^{iH_{bA}t^{}/\mathrm{}}e^{i(H_{bA}+B__A)t^{}/\mathrm{}}e^{\beta H_{bA}}\right\}`$
$`\times {\displaystyle \frac{1}{Z_{bD}^{}}}Tr_{bD}\{e^{i(H_{bD}+B__D)t^{}/\mathrm{}}e^{iH_{bD}t^{}/\mathrm{}}`$
$`\times e^{\beta (H_{bD}+B_D)}\}]\text{ }\text{.}`$
The derivation of this expression can be made by rewriting $`e^{i(H_{bD}+B_D)t/\mathrm{}}`$ in Eq. (18) as $`e^{i(H_{bD}+B_D)(tt^{})/\mathrm{}}e^{i(H_{bD}+B_D)t^{}/\mathrm{}}`$, using the cyclic symmetry of the trace operation for the first term, and then finally imposing the replacement of Eq. (20).

The second is the infinite time approximation. That is, the FD rate corresponds to the following limit:

$$k_{_{FD}}=k_r(\mathrm{})\text{ }\text{.}$$
(25)
This approximation is valid if there is time scale separation between the bath dynamics and the EET kinetics.

For practical purposes of evaluating the reaction rate for real systems, it is important to find the explicit expression for Eq. (18) in the frequency domain as an overlap of independent spectral profiles of the donor and of the acceptor. Considering the fact that the term involving the acceptor is identical in Eqs. (18) and (24), one can expect that the nonequilibrium EET rate also involves the stationary absorption profile of the acceptor. For this purpose, we define the absorption profile of the acceptor as

$`I_A(\omega )`$ $`=`$ $`|𝝁_𝑨\widehat{𝐞}|^2{\displaystyle _{\mathrm{}}^{\mathrm{}}}dte^{i\omega tiϵ__At/\mathrm{}}{\displaystyle \frac{1}{Z_{bA}}}Tr_{bA}\{e^{iH_{bA}t/\mathrm{}}`$ (27)
$`\times e^{i(H_{bA}+B__A)t/\mathrm{}}e^{\beta H_{bA}}\}\text{ }\text{,}`$
where $`𝝁_𝑨`$ is the transition dipole of the acceptor and $`\widehat{𝐞}`$ is the polarization vector of the radiation. Inserting the inverse transform of this into Eq. (18),

$`k(t)={\displaystyle \frac{J^2}{\pi \mathrm{}^2|𝝁_𝑨\widehat{𝐞}|^2}}{\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑\omega I_A(\omega )`$ (28)
$`\times \mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i\omega t^{}+iϵ__Dt^{}/\mathrm{}}{\displaystyle \frac{1}{Z_{bD}}}Tr_{bD}\{e^{i(H_{bD}+B__D)t/\mathrm{}}`$ (29)
$`\times e^{iH_{bD}t^{}/\mathrm{}}e^{i(H_{bD}+B__D)(tt^{})/\mathrm{}}e^{\beta H_{bD}}\}]\text{ }\text{.}`$ (30)
The time dependent part involving the donor can be expressed as the stimulated emission profile in a pump-probe experiment. In Appendix A, we derive a time dependent stimulated emission profile of the donor which is subject to a stationary field after being excited by a delta pulse. Inserting Eq. (A10) into Eq. (30), the frequency domain expression of the EET rate is given by

$$k(t)=\frac{J^2}{2\pi \mathrm{}^2|𝝁_𝑨\widehat{𝐞}|^2|𝝁_𝑫\widehat{𝐞}|^2}_{\mathrm{}}^{\mathrm{}}𝑑\omega I_A(\omega )E_D(t,\omega )\text{ }\text{.}$$
(31)
In the limit where $`t\mathrm{}`$, this expression becomes equivalent to the Förster’s spectral overlap expression as long as $`E_D(\mathrm{},\omega )`$ is equal to the spontaneous emission profile of the excited donor except for a normalization factor and the universal frequency dependent scaling function.

Equation (31) is the central result of the present paper. It is the pump-probe version of the hot transfer rate and generalizes the spectral overlap expression of Förster for fast EET processes. With the modern development of ultrafast spectroscopy, determination of $`k(t)`$ and $`E_D(t,\omega )`$ can be made even in femtosecond scale. With the advances in experimental techniques of altering chromophores by chemical or biological manipulations, independent determinations of $`I_A(\omega )`$ and $`E_D(t,\omega )`$ can be done at the same condition as that of $`k(t)`$ for a broad range of systems. If these practical issues are settled and if the system satisfies the requirements for applying the perturbation theory, Eq. (31) should hold as long as the effect of common modes is insignificant.

In Eq. (LABEL:eq:kt1), we have defined the reaction rate as the time derivative of $`P_A(t)`$. Due to the use of perturbation theory, such a definition gives a valid result only for $`_0^t𝑑t^{}k(t^{})<<1`$. In the longer time limit when the population transfer has occurred significantly, instead, the reaction rate should be understood as the exponential decay rate of $`1P_A(t)`$. The justification for this comes from the Redfield-type equation and the assumption that the bath relaxation has been completed. A reasonable way of combining these two limits is to exponentiate the time integration of $`k(t)`$ as follows:

$$P_A(t)1\mathrm{exp}\left(_0^t𝑑t^{}k(t^{})\right)\text{ }\text{,}$$
(32)
where it has been assumed that the transfer from $`D`$ to $`A`$ is irreversible due to either energetic or entropic reason. Equation (32) is not based on a rigorous derivation, and conditions when such approximation is valid need to be clarified based on a more rigorous approach, which will be done elsewhere. However, for the purpose of understanding the qualitative aspect of EET kinetics in the nonequilibrium situation, which is the main purpose of the present paper, the expression of Eq. (32) is useful.

### B Linearly coupled harmonic oscillator bath

For the simple case where the bath consists of independent harmonic oscillators, an explicit expression can be found for $`k(t)`$. Assume that the bath Hamiltonian is given by

$$H_b=\underset{n}{}\mathrm{}\omega _n\left(b_n^{}b_n+\frac{1}{2}\right)\text{ }\text{,}$$
(33)
and the chromophore-bath interaction is linear in the bath coordinate as follows:

$$H_{eb}=\underset{n}{}\mathrm{}\omega _n(b_n+b_n^{})(g_{nD}a__D^{}a__D+g_{nA}a__A^{}a__A)\text{ }\text{,}$$
(34)
where $`g_{nD}g_{nA}=0`$ and thus the condition of Eq. (4) is satisfied. For an explicit calculation, it is convenient to start from Eq. (18). The integrand of the reaction rate involves trace of the product of the propagators for displaced harmonic oscillators. Each trace over the acceptor bath and the donor bath can be done explicitly, and the resulting expression for the reaction rate can be written as

$`k(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}i_n(g_{nD}^2+g_{nA}^2)\mathrm{sin}(\omega _nt^{})}`$ (37)
$`\times e^{2i_ng_{nD}^2(\mathrm{sin}(\omega _nt)\mathrm{sin}(\omega _n(tt^{}))}`$
$`\times e^{2_n(g_{nD}^2+g_{nA}^2)\mathrm{coth}(\beta \mathrm{}\omega _n/2)\mathrm{sin}^2(\omega _nt^{}/2)}]\text{ }\text{,}`$
where

$`\stackrel{~}{ϵ}_{D(A)}`$ $`=`$ $`ϵ_{D(A)}{\displaystyle \underset{n}{}}\mathrm{}\omega _ng_{nD(A)}^2`$ (38)
$``$ $`ϵ_{D(A)}\lambda _{D(A)}\text{ }\text{,}`$ (39)
where $`\lambda _D`$ and $`\lambda _A`$ are reorganization energies of the donor and acceptor baths. For the harmonic oscillator bath model, in fact, the reaction rate can be calculated explicitly even for more general situation where there are common modes coupling both the donor and acceptor. In Appendix B, we derive the general expression employing the small polaron transformation. Equation (37) can alternatively be obtained from Eq. (B20) by letting $`g_{nD}g_{nA}=0`$.

Define the following spectral densities:

$`\eta _D(\omega )`$ $``$ $`{\displaystyle \underset{n}{}}g_{nD}^2\omega _n^2\delta (\omega \omega _n)\text{ }\text{,}`$ (40)
$`\eta _A(\omega )`$ $``$ $`{\displaystyle \underset{n}{}}g_{nA}^2\omega _n^2\delta (\omega \omega _n)\text{ }\text{.}`$ (41)
Inserting these definitions into Eq. (37), the nonequilibrium EET rate can be expressed as

$`k(t)`$ $`={\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}}`$ (45)
$`\times e^{i_0^{\mathrm{}}𝑑\omega (\eta _D(\omega )+\eta _A(\omega ))\mathrm{sin}(\omega t^{})/\omega ^2}`$
$`\times e^{2i_0^{\mathrm{}}𝑑\omega \eta _D(\omega )(\mathrm{sin}(\omega t)\mathrm{sin}(\omega (tt^{})))/\omega ^2}`$
$`\times e^{2_0^{\mathrm{}}𝑑\omega (\eta _D(\omega )+\eta _A(\omega ))\mathrm{coth}(\beta \mathrm{}\omega /2)\mathrm{sin}^2(\omega t^{}/2)/\omega ^2}].`$
This is the main result of the present subsection. The expression for $`k_r(t)`$, which can be calculated from Eq. (24) through a similar procedure is given by

$`k_r(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}}`$ (49)
$`\times e^{i_0^{\mathrm{}}𝑑\omega (\eta _D(\omega )+\eta _A(\omega ))\mathrm{sin}(\omega t^{})/\omega ^2}`$
$`\times e^{2_0^{\mathrm{}}𝑑\omega (\eta _D(\omega )+\eta _A(\omega ))\mathrm{coth}(\beta \omega /2)\mathrm{sin}^2(\omega t^{}/2)/\omega ^2}].`$
Due to the nonstationary initial condition, the integrand in Eq. (LABEL:eq:kt5) has an additional dependence on $`t`$, which becomes clear when we compare the expression with that of $`k_r(t)`$. In general, further simplifications of the rate expressions given by Eqs. (LABEL:eq:kt5) and (LABEL:eq:krt-2) cannot be made. However, this does not pose a practical difficulty in calculating the reaction rate because direct numerical integrations of these expressions can be done quite easily. In the next section, we implement these calculations for a simple model spectral density.

Before concluding this section, we examine one important limit where the stationary phase approximation is possible. In the strong excitation-bath coupling or high temperature limit, the dominant contribution of the integration comes from small $`t^{}`$ region. Expanding all the functions of $`t^{}`$ in the exponent up to the second order, Eq. (LABEL:eq:kt5) can be approximated as

$`k_s(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}\left[{\displaystyle _0^t}𝑑t^{}e^{i(\delta \stackrel{~}{ϵ}\lambda _T+2C(t))t^{}/\mathrm{}(D(\beta )/2iS(t))t^2}\right]`$ (51)
$`=`$ $`2J^2\mathrm{Re}[e^{(\delta \stackrel{~}{ϵ}\lambda _T+2C(t))^2/(2\mathrm{}^2(D(\beta )2iS(t)))}`$ (53)
$`\times {\displaystyle _0^t}dt^{}e^{(D(\beta )/2iS(t))\left(t^{}i\frac{(\delta \stackrel{~}{ϵ}\lambda _T+2C(t))}{\mathrm{}(D(\beta )2iS(t))}\right)^2}]\text{ }\text{,}`$
where

$`\lambda _T`$ $``$ $`\mathrm{}{\displaystyle _0^{\mathrm{}}}𝑑\omega {\displaystyle \frac{\eta _D(\omega )+\eta _A(\omega )}{\omega }}=\lambda _D+\lambda _A\text{ }\text{,}`$ (55)
$`S(t)`$ $``$ $`{\displaystyle _0^{\mathrm{}}}𝑑\omega \eta _D(\omega )\mathrm{sin}(\omega t)\text{ }\text{,}`$ (56)
$`C(t)`$ $``$ $`\mathrm{}{\displaystyle _0^{\mathrm{}}}𝑑\omega {\displaystyle \frac{\eta _D(\omega )}{\omega }}\mathrm{cos}(\omega t)\text{ }\text{,}`$ (57)
$`D(\beta )`$ $``$ $`{\displaystyle _0^{\mathrm{}}}𝑑\omega (\eta _D(\omega )+\eta _A(\omega ))\mathrm{coth}({\displaystyle \frac{\beta \mathrm{}\omega }{2}})\text{ }\text{.}`$ (58)
Although Eq. (53) involves a simpler integration than Eq. (LABEL:eq:kt5), the complex Gaussian integration for finite $`t`$ does not convey a clear physical picture. If $`|S(t)|<<D(\beta )`$ and in the long enough time limit, one can disregard the imaginary term $`S(t)`$ and approximate the integration in Eq. (53) as that from $`0`$ to $`\mathrm{}`$. The rate expression under this situation can be simplified as

$$k_{sg}(t)=\frac{J^2}{\mathrm{}^2}\sqrt{\frac{2\pi }{D(\beta )}}e^{(\delta \stackrel{~}{ϵ}\lambda _T+2C(t))^2/2\mathrm{}^2D(\beta )}\text{ }\text{.}$$
(59)
This approximation is valid only for long time regime and for strong enough excitation-bath coupling. The maximum rate based on this expression is obtained for $`\delta \stackrel{~}{ϵ}=\lambda _T2C(t)`$. Since $`C(\mathrm{})=0`$ for most realistic spectral densities (cf. sub-Ohmic, $`C(\mathrm{})0`$), this relation implies that the optimum energy difference in the long time limit is given by $`\delta \stackrel{~}{ϵ}=\lambda _T`$. However, the above expression suggests that the reaction rate for a nonoptimum $`\delta \stackrel{~}{ϵ}`$ can also be substantial during the transient period when $`C(t)`$ changes. If $`J`$ is not small compared to the bath relaxation rate, the contribution of this transient term cannot be neglected. A similar observation was made in the theory of nonequilibrium electron transfer reaction.

## III Model calculations

Assume that the bath modes coupled to $`D`$ and $`A`$ have the same spectral profile, while their magnitudes of coupling can be different. We consider a model where the number of modes increases linearly for small $`\omega `$ and has an exponential tail for large $`\omega `$. The corresponding spectral densities, defined by Eqs. (40) and (41), thus have the following form:

$`\eta _{_{D(A)}}(\omega )`$ $`=`$ $`\alpha _{_{D(A)}}{\displaystyle \frac{\omega ^3}{\omega _c^2}}e^{\omega /\omega _c}\text{ }\text{,}`$ (60)
where $`\alpha __D`$ and $`\alpha __A`$ determine the coupling strengths of $`|D`$ and $`|A`$ to their respective bath modes. $`\omega _c`$ is the cutoff frequency which determines the spectral range of the bath. Due to the common value of this cutoff frequency, the bath relaxation dynamics has a single time scale and the reaction rate exhibits a simple scaling behavior. In Appendix C, we provide a detailed form of the reaction rate in the units where $`\mathrm{}=1`$. As can be seen from Eq. (C1), all the EET kinetics for different $`\omega _c`$ can be deduced from the following dimensionless rate:

$$\kappa (\tau )=\frac{\omega _c}{J^2}k(t)\text{ }\text{,}\tau =\omega _ct$$
(61)
For the case where the reaction rate is time dependent, the instantaneous value of the reaction rate cannot be a clear indication of the efficiency of the energy transfer. For this reason, we also provide the following dimensionless quantity:

$$p(\tau )=_0^\tau 𝑑\tau ^{}\kappa (\tau ^{})\text{ }\text{.}$$
(62)
According to Eq. (32), $`P_A(t)1\mathrm{exp}\{(J/\omega _c)^2p(\tau )\}`$, the population of $`|A`$ at time $`t=\tau /\omega _c`$.

For the reaction rate $`k_r(t)`$ given by Eq. (LABEL:eq:krt-2), similar quantities can be defined and these are denoted as $`\kappa _r(\tau )`$ and $`p_r(\tau )`$. The expression for $`\kappa _r(\tau )`$ can be obtained from that of $`\kappa (\tau )`$ simply disregarding the third term in Eq. (C3). Equations (C8)-(C12) in combination with Eqs. (53) and (59) provide explicit expressions for $`k_s(t)`$ and $`k_{sg}(t)`$. The dimensionless versions of these rates are denoted as $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$, and their cumulative integrations are represented by $`p_s(\tau )`$ and $`p_{sg}(\tau )`$.

### A Zero temperature limit

We first performed calculations for $`\alpha _D=\alpha _A=10`$, a strong coupling limit. The values of the renormalized energy difference $`\delta \stackrel{~}{ϵ}`$ were chosen to be $`\lambda _T\lambda _D`$, $`\lambda _T`$, and $`\lambda _T+\lambda _D`$, which were motivated by the form of Eq. (59). These three cases are analogues of the normal, activationless, and inverted regimes in the electron transfer kinetics. Figure 1 shows the rates. The nonequilibrium effect is shown to be important until about $`\tau 2`$. This is in contrast to the behavior of $`\kappa _r(\tau )`$, which approaches the long time limit in about $`\tau 0.2`$. During the nonstationary period, $`\kappa (\tau )`$ goes through a maximum before approaching the long time limit in a smooth fashion. The maximum value appears earlier for smaller value of $`\delta \stackrel{~}{ϵ}`$, for which it takes shorter for the bath to relax into the resonance condition. In the classical limit, this can be understood in terms of the average time for the wavepacket in the excited state to go through the crossing point.

The two approximations of $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$ reproduce the long time limit quite well for the present case of strong coupling limit. In the nonstationary regime, they exhibit a qualitative behavior similar to that of $`\kappa (\tau )`$, but the quantitative agreement is not satisfactory in the region of $`1<\tau <2`$. This indicates that, in this intermediate time regime, the coherence of the bath still plays a substantial role and cannot be well approximated by the stationary phase integration.

In Fig. 2, $`p(\tau )`$ given by Eq. (62) and analogous quantities for other approximations are provided. For $`\delta \stackrel{~}{ϵ}=\lambda _T\lambda _D`$, the nonequilibrium contribution results in larger population transfer during the short initial period, but not in the longer time period. For $`\delta \stackrel{~}{ϵ}=\lambda _T`$, the nonequilibrium effect always leads to smaller population transfer. For $`\delta \stackrel{~}{ϵ}=\lambda _T+\lambda _D`$, the nonequilibrium population transfer is smaller than the fully relaxed one until about $`\tau 1`$, but it becomes larger during the longer time as the delayed response of the bath brings a resonance condition. The different kinetics during the nonstationary period is seen to result in finite differences in the net population transfer in the long time regime. The values of $`p_s(\tau )`$ and $`p_{sg}(\tau )`$ are seen to overestimate $`p(\tau )`$ when $`\delta \stackrel{~}{ϵ}=\lambda _T\lambda _D`$ and underestimates it for $`\delta \stackrel{~}{ϵ}=\lambda _T+\lambda _D`$. The stationary phase approximation seems to work relatively well for the case of $`\delta \stackrel{~}{ϵ}=\lambda _T`$.

Some of the patterns observed from the above calculations may be specific for the model of the bath and the temperature. However, the features that the nonequilibrium effect is substantial until about up to $`\tau 2`$ and that the maximum peak of the reaction rate appears earlier for smaller $`\delta \stackrel{~}{ϵ}`$ are expected to hold quite generally. Due to the assumption of strong coupling, the approximate expressions of $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$ agree quite well with $`\kappa (\tau )`$, although there is still a difference in the net population. Such agreement cannot be seen for the weak coupling case considered next, an expected result considering the assumptions involved in $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$.

Calculations were performed for $`\alpha _D=1`$ and $`\alpha _A=1`$, a weak coupling limit. Figure 3 shows the dimensionless reaction rates and Fig. 4 their cumulative integrations. Unlike the case of strong coupling, the difference between $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$ is not appreciable except for some phase difference in their oscillations. The resulting time integrations, $`p(\tau )`$ and $`p_r(\tau )`$, are quite close as can be seen from Fig. 4. Especially for the two cases of $`\delta \stackrel{~}{ϵ}=\lambda _T`$ and $`\delta \stackrel{~}{ϵ}=\lambda _T+\lambda _D`$, the two curves almost overlap with each other. The approximations of $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$ are not expected to work well for the present weak coupling regime, but it is meaningful to examine their qualitative nature. In Fig. 3 , it is shown that $`\kappa _s(\tau )`$ and $`\kappa _{sg}(\tau )`$ do not reproduce the oscillatory behavior and deviate from $`\kappa (\tau )`$ systematically, except for the case of $`\delta \stackrel{~}{ϵ}=\lambda _T`$. The resulting values of $`p_s(\tau )`$ and $`p_{sg}(\tau )`$ underestimate $`p(\tau )`$ for $`\delta \stackrel{~}{ϵ}=\lambda _T\lambda _D`$ and overestimate it for $`\delta \stackrel{~}{ϵ}=\lambda _T+\lambda _D`$. These are opposite to the trends observed for strong coupling limit. In conclusion, for the present case of weak coupling, the nonequilibrium effect is unimportant, and both $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$ rise to their steady state limit in a similar fashion. The oscillations persistent in both $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$ in Fig. 3 originate from $`e^{i(ϵ__Dϵ__A)t^{}/\mathrm{}}`$ in Eqs. (LABEL:eq:kt5) and (LABEL:eq:krt-2), which remains significant even in the long time limit due to the weak excitation-bath coupling. However, even though all the assumptions of the present section hold, actual observation of these oscillations in a real system is unlikely due to the energy uncertainty related dephasing.

### B Temperature effect

As the temperature increases, the phonon side band becomes broader in the spectral overlap expression of Eq. (31). The relaxation and dephasing of the bath become faster also. It is interesting to examine how these changes affect the nonequilibrium kinetics. For this purpose, we compare only $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$. The temperature dependence was accounted for by using an approximate expression for $`\gamma (\tau )`$, in Eq. (C1), as follows:

$`\gamma (\tau )`$ $``$ $`(\alpha _D+\alpha _A)({\displaystyle \frac{\tau ^2}{1+\tau ^2}}+{\displaystyle \frac{2\tau ^2}{(1+\tau ^2)^2}}`$ (64)
$`+{\displaystyle \frac{16\tau ^2}{\beta \omega _c(\beta \omega _c+2)((\beta \omega _c+2)^2+4\tau ^2)}})\text{ }\text{.}`$
This is based on the approximation of $`\mathrm{coth}(x/2)1+(2/x)e^{x/2}`$, which reproduces the proper low and high temperature limits. Although the approximation is rather crude in the region of $`\beta \omega _c1`$, the overall performance is good enough to produce a correct qualitative trend.

In Fig. 5, we provide results for $`\alpha _D=\alpha _A=10`$, the strong coupling limit, and for $`\delta \stackrel{~}{ϵ}=\lambda _T\lambda _D`$. The zero temperature result is shown in the top panel of Fig. 1. As the temperature increases, the nonequilibrium effects diminish. However, even for very high temperature limit of $`\beta \omega _c=0.1`$, there is a noticeable difference between $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$. Only in the highest temperature limit of $`\beta \omega _c=0.01`$, $`\kappa (\tau )`$ and $`\kappa _r(\tau )`$ show an agreement. This indicates that for strongly coupled systems, the nonequilibrium effects persist even up to very high temperature. Next, we considered the weak coupling case of $`\alpha _D=\alpha _A=1`$ with the same choice of $`\delta \stackrel{~}{ϵ}=\lambda _T\lambda _D`$. The results are shown in Fig. 6. In the zero temperature limit, the nonequilibrium effect was not so significant for this weak coupling case. This fact remains the same even for the higher temperature.

## IV Discussion

The main focus of the present paper was the nonequilibrium bath relaxation effect. For this reason, we considered only the simplest case where donor and acceptor each have one excited state. However, as recent studies on various systems indicate, the existence of multiple chromophores is a general situation rather than an exception. Therefore, one in general must consider the case where the donor and the acceptor respectively consist of multiple exciton states. Given that the inter-excitonic relaxation can be disregarded or approximated in a self consistent way, the generalization of the present theory can be done straightforwardly as are those of the FD theory. In many cases, this type of simple extension may indeed capture the main aspect of the EET between multichromorphic donor and acceptor. However, if some of the excitonic levels are closely spaced or if there is degeneracy due to symmetry, more careful theoretical analysis is necessary.

In a heterogeneous environment or a complex system, disorder plays an important role and its explicit consideration becomes necessary for a proper understanding of the system. Due to the averaging over the static disorder involved in this case, our spectral overlap expression cannot be used directly for the observables of an ensemble experiment. However, given that the distribution of the static disorder is well characterized by other means, Monte Carlo simulation can provide an indirect way of determining the nonequilibrium population transfer. The study of the interplay between the heterogeneity and the nonequilibrium effect in this way can bring new insights into the fast EET kinetics of complex systems.

In the LH2 of purple bacteria, the EET from B800 to B850 occurs in about $`1\mathrm{p}\mathrm{s}`$ and the rate is not so sensitive to temperature. This rate is much faster than that obtained by the FD theory, but it has recently been shown that consideration of the multichromorphic nature of the B850 and the disorder account for much of the discrepancy. However, the theoretical value is still somewhat smaller than the experimental one. Many explanations are possible for this, and the nonequilibrium effect is one such possibility.

According to our model calculations, the nonequilibrium short time kinetics shows complicated time dependent behavior and the reaction rate in this regime is less dependent on the spectral overlap between the stationary emission and absorption profiles. Some of these features can be seen in recent sub-picosecond pump-probe experiments. For example, the reaction rate is shown to be relatively insensitive to the change of the spectral profile for the EET in the photosynthetic reaction center.

Before applying the present theory to a given system, it is always important to examine whether the nature of the system is consistent with the assumption of irreversibility and the use of second order approximation. It is expected that our results can be applied as long as $`\delta \stackrel{~}{ϵ}`$ is sufficiently large and the bath relaxation of the acceptor is fast enough. However, in order to address these issues more systematically, it is necessary to formulate a theory that can account for electronic coherence. For this purpose, one may adopt the formalism of the generalized master equation or consider in the framework of the Redfield-type equation.

###### Acknowledgements.

SJ thanks Prof. R. M. Hochstrasser for discussions on the EET and pump-probe experiments.

## A Time dependent stimulated emission profile of the donor

Consider a system consisting of the donor and its own bath. The relevant Hamiltonian in the single excitation manifold is given by

$$H_D=ϵ__Da__D^{}a__D+B__Da__D^{}a__D+H_{b_D}\text{ }\text{.}$$
(A1)
Assume that the donor is excited at time zero by a delta pulse. Then, the initial density operator at $`t=0`$ is given by

$$\rho (0)=|DD|\frac{1}{Z_{b_D}}e^{\beta H_{b_D}}\text{ }\text{.}$$
(A2)
Right after the pulse excitation, a stationary field with a fixed frequency $`\omega `$ is turned on. The time dependent Hamiltonian governing the dynamics for $`t>0`$, assuming unit field strength, is given by

$$H(t)=H_D+|𝝁_𝑫\widehat{𝐞}|(e^{i\omega t}|Dg|+e^{i\omega t}|gD|)\text{ }\text{,}$$
(A3)
where rotating wave approximation was used. The probability for the donor to emit a photon and go to the ground state, induced by the stationary field, is given by

$`P_g(t)=|𝝁_𝑫\widehat{𝐞}|^2{\displaystyle _0^t}𝑑t^{}{\displaystyle _0^t}𝑑t^{\prime \prime }e^{i\omega (t^{}t^{\prime \prime })iϵ__D(t^{}t^{\prime \prime })/\mathrm{}}`$ (A4)
$`\times {\displaystyle \frac{1}{Z_{b_D}}}Tr_{b_D}\{e^{iH_{b_D}(tt^{})/\mathrm{}}e^{i(B_D+H_{b_D})t^{}/\mathrm{}}`$ (A5)
$`\times e^{\beta H_{b_D}}e^{i(B_D+H_{b_D})t^{\prime \prime }/\mathrm{}}e^{iH_{b_D}(tt^{\prime \prime })/\mathrm{}}\}\text{ }\text{,}`$ (A6)
where weak field approximation was used. The time dependent stimulated emission profile is defined as the time derivative of this probability as follows:

$`E_D(t,\omega )`$ $``$ $`{\displaystyle \frac{d}{dt}}P_g(t)`$ (A7)
$`=`$ $`2|𝝁_𝑫\widehat{𝐞}|^2\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i\omega t^{}+iϵ__Dt^{}/\mathrm{}}`$ (A10)
$`\times {\displaystyle \frac{1}{Z_{b_D}}}Tr_{b_D}\{e^{i(H_{b_D}+B_D)t/\mathrm{}}e^{iH_{b_D}t^{}/\mathrm{}}`$
$`\times e^{i(H_{b_D}+B_D)(tt^{})/\mathrm{}}e^{\beta H_{b_D}}\}]\text{ }\text{.}`$
## B rate expression for a general harmonic oscillator bath

For a general harmonic oscillator bath model, we derive the expression of the nonequilibrium reaction rate given by Eq. (LABEL:eq:kt1) based on the small polaron transformation. For this purpose, first we introduce the following generator of small polaron transformation:

$$S=\underset{n}{}(b_nb_n^{})(g_{nD}a__D^{}a__D+g_{nA}a__A^{}a__A)\text{ }\text{.}$$
(B1)
Then, it is straightforward to show that

$`\stackrel{~}{H}=e^SHe^S`$ $`=`$ $`\stackrel{~}{ϵ}__Da__D^{}a__D+\stackrel{~}{ϵ}__Aa__A^{}a__A+H_b+\stackrel{~}{H}_{DA}`$ (B2)
$`=`$ $`\stackrel{~}{H}_0+\stackrel{~}{H}_{DA}\text{ }\text{,}`$ (B3)
where

$`\stackrel{~}{H}_{DA}`$ $`=`$ $`Je^S(a__D^{}a__A+a__A^{}a__D)e^S`$ (B4)
$`=`$ $`J(\theta _D^{}\theta _Aa__D^{}a__A+\theta _A^{}\theta _Da__A^{}a__D)\text{ }\text{,}`$ (B5)
where

$$\theta _{D(A)}^{}=e^{_ng_{nD(A)}(b_nb_n^{})}\text{ }\text{.}$$
(B6)
Inserting $`1=e^Se^S`$ between every two operators in Eq. (LABEL:eq:kt1), one can show that

$`k(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}}`$ (B8)
$`\times {\displaystyle \frac{1}{Z_b}}Tr_b\left\{e^{iH_bt^{}/\mathrm{}}\mathrm{\Theta }^{}e^{iH_bt^{}/\mathrm{}}\mathrm{\Theta }\rho _d(tt^{})\right\}]\text{ }\text{,}`$
where $`\mathrm{\Theta }^{}=\theta _D^{}\theta _A`$,

$`\rho _d(t)`$ $``$ $`e^{iH_bt/\mathrm{}}\theta _D^{}e^{\beta H_b}\theta _De^{iH_bt/\mathrm{}}`$ (B9)
$`=`$ $`e^{\beta _n\mathrm{}\omega _n(\stackrel{~}{b}_{nD}^{}(t)\stackrel{~}{b}_{nD}(t)+\frac{1}{2})}\text{ }\text{,}`$ (B10)
with

$$\stackrel{~}{b}_{nD}(t)b_ng_{nD}e^{i\omega _nt}\text{ }\text{.}$$
(B11)
In Eq. (B8),

$`e^{iH_bt/\mathrm{}}\mathrm{\Theta }^{}e^{iH_bt/\mathrm{}}`$ (B12)
$`=\mathrm{exp}\left\{{\displaystyle \underset{n}{}}g_{n\mathrm{\Delta }}(b_ne^{i\omega _nt}b_n^{}e^{i\omega _nt})\right\}\text{ }\text{,}`$ (B13)
where $`g_{n\mathrm{\Delta }}g_{nD}g_{nA}`$. Inserting Eqs. (B10)-(B13) into Eq. (B8),

$`k(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}}e^{i_ng_{n\mathrm{\Delta }}\mathrm{sin}(\omega _nt^{})}`$ (B17)
$`\times e^{2i_ng_{n\mathrm{\Delta }}g_{nD}(\mathrm{sin}(\omega _nt)\mathrm{sin}(\omega _n(tt^{})))}`$
$`\times {\displaystyle \frac{1}{Z_b}}Tr_b\{e^{_ng_{n\mathrm{\Delta }}((e^{i\omega _nt^{}}1)\stackrel{~}{b}_{nD}(e^{i\omega _nt^{}}1)\stackrel{~}{b}_{nD}^{})}`$
$`\times e^{\beta _n\mathrm{}\omega _n(\stackrel{~}{b}_{nD}^{}\stackrel{~}{b}_{nD}+\frac{1}{2})}\}]\text{ }\text{,}`$
where the time dependences of $`\stackrel{~}{b}_{nD}(tt^{})`$ and $`\stackrel{~}{b}_{nD}^{}(tt^{})`$ have been omitted, but this does not make any difference in the result because of the trace operation. Disentangling the summation in the exponent and then evaluating the trace over the bath, one can reduce Eq. (B17) into the following integral expression:

$`k(t)`$ $`=`$ $`{\displaystyle \frac{2J^2}{\mathrm{}^2}}\mathrm{Re}[e^{2i_ng_{n\mathrm{\Delta }}g_{nD}\mathrm{sin}(\omega _nt)}{\displaystyle _0^t}dt^{}e^{i(\stackrel{~}{ϵ}__D\stackrel{~}{ϵ}__A)t^{}/\mathrm{}}`$ (B20)
$`\times e^{i_ng_{n\mathrm{\Delta }}^2\mathrm{sin}(\omega _nt^{})2i_ng_{n\mathrm{\Delta }}g_{nD}\mathrm{sin}(\omega _n(tt^{}))}`$
$`\times e^{2_ng_{n\mathrm{\Delta }}^2\mathrm{coth}(\beta \mathrm{}\omega _n/2)\mathrm{sin}^2(\omega _nt^{}/2)}]\text{ }\text{.}`$
For the case where there is no common mode, $`g_{n\mathrm{\Delta }}g_{nD}=g_{nD}^2`$ and $`g_{n\mathrm{\Delta }}^2=g_{nD}^2+g_{nA}^2`$ and the expression of Eq. (37) is reproduced.

## C Rate expressions for the model spectral densities of Sec. III

For the spectral densities given by Eq. (60), the integrations within the exponents of Eq. (LABEL:eq:kt5) can be performed explicitly. Adopting the units where $`\mathrm{}=1`$, the reaction rate of Eq. (LABEL:eq:kt5) can be expressed as

$$k(t)=\frac{2J^2}{\omega _c}\mathrm{Re}\left[_0^\tau 𝑑\tau ^{}e^{i\varphi (\tau ,\tau ^{})\gamma (\tau ^{})}\right]\text{ }\text{,}$$
(C1)
where $`\tau =\omega _ct,\tau ^{}=\omega _ct^{}`$, and

$`\varphi (\tau ,\tau ^{})`$ $`=`$ $`\left({\displaystyle \frac{ϵ__Dϵ__A}{\omega _c}}2(\alpha __D\alpha __A)\right)\tau ^{}{\displaystyle \frac{2(\alpha __D+\alpha __A)\tau ^{}}{(1+\tau ^2)^2}}`$ (C3)
$`4\alpha __D\left({\displaystyle \frac{\tau \tau ^{}}{(1+(\tau \tau ^{})^2)^2}}{\displaystyle \frac{\tau }{(1+\tau ^2)^2}}\right)\text{ }\text{.}`$
In Eq. (C1), the function $`\gamma (\tau ^{})`$ comes from the integration involving $`\mathrm{coth}(\beta \omega \mathrm{}/2)`$ in Eq. (LABEL:eq:kt5). Simple approximation for this function is possible in the limits of low and high temperature. Using these approximations,

$`\gamma (\tau )`$ $`=\{\begin{array}{c}(\alpha __D+\alpha __A)\left(\frac{\tau ^2}{1+\tau ^2}+\frac{2\tau ^2}{(1+\tau ^2)^2}\right),\beta \omega _c>>1\text{ }\text{,}\\ \frac{2(\alpha __D+\alpha __A)}{\omega _c\beta }\frac{\tau ^2}{1+\tau ^2},\beta \omega _c<<1\text{ }\text{.}\end{array}`$ (C6)
In the main text, we consider the zero temperature limit first and study the finite temperature effect using a simple interpolation formula. Similarly, the quantities entering the approximate rate expressions of Eqs. (53) and (59) can be calculated. These are

$`\lambda _T`$ $`=`$ $`2(\alpha __D+\alpha __A)\omega _c\text{ }\text{,}`$ (C7)
$`S(t)`$ $`=`$ $`24\alpha __D\omega _c^2{\displaystyle \frac{\tau \tau ^3}{(1+\tau ^2)^4}}\text{ }\text{,}\tau =\omega _ct\text{ }\text{,}`$ (C8)
$`C(t)`$ $`=`$ $`2\alpha __D\omega _c{\displaystyle \frac{1\tau ^2}{(1+\tau ^2)^3}}\text{ }\text{,}\tau =\omega _ct\text{ }\text{,}`$ (C9)
$`D(\beta )`$ $`=`$ $`\{\begin{array}{c}6(\alpha __D+\alpha __A)\omega _c^2,\beta \omega _c>>1\text{ }\text{,}\\ 4(\alpha __D+\alpha __A)\omega _c/\beta ,\beta \omega _c<<1\text{ }\text{.}\end{array}`$ (C12)