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For a real vector $\mathbf{r}$, the direction is given by: $\hat{\mathbf{n}}=\mathbf{r}/\left|\mathbf{r}\right|$.

The transition dipole moment is a complex vector. How do you define its direction?

The point of this question is that I am trying to understand the meaning of equation 9.29 of the book Charge and Energy Transfer 3rd Ed by May & Kuhn, which reads:

$$J_{mn}=\frac{\left|\mathbf{d}_{m}\right|\left|\mathbf{d}_{n}^{*}\right|}{R_{mn}^3}\left[\mathbf{n}_{m}\cdot\mathbf{n}_{n}-3\left(\mathbf{e}_{mn}\cdot\mathbf{n}_{m}\right)\left(\mathbf{e}_{mn}\cdot\mathbf{n}_{n}\right)\right]$$

In the next paragraph I attempt to explain the notation in this equation. I'll point out the parts that confuse me.

Here we are considering two molecules labeled $m$ and $n$, and we only consider two electronic levels in each, the ground state $g$ and one excited state $e$. $\mathbf{d}_{m}$ is the transition dipole moment for the transition $g\rightarrow e$ of the $m$th molecule, and similarly for $\mathbf{d}_{n}$. $\mathbf{n}_{m}$ is a unit vector pointing in the direction of $\mathbf{d}_{n}$ (I don't understand this), and similarly for $\mathbf{n}_{n}$. Finally, $R_{mn}$ is the distance between the centers of mass of the molecules. The quantity we are calculating here, $J_{mn}$, is the excitonic coupling between the two molecules. This can be seen as the rate at which an exciton at a molecule $n$ will be transfered to a molecule $m$ initially in its ground state. Here we calculate $J_{mn}$ using the dipole-dipole interaction approximation, valid when the molecules are sufficiently far apart.

Note also the factor $\left|\mathbf{d}_{n}^{*}\right|$ in the equation. I don't understand this bit of notation either. I am not sure how to interpret the complex conjugation sign ($*$) as it appears inside absolute-value brackets ($|\square |$).

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1 Answer

Typically the basis wave functions are real, so the transition dipole moment is real too. But if it was complex, then it still can be written as product of magnitude and unit vector n, which then represents its "direction".

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Could you expand this answer a bit more for the benefit of the OP?! – michielm Apr 13 at 7:55
Agree with @michielm. Can you explain? In what setting are the wave functions real? If it isn't real, the unit vector n is a complex vector. What's the meaning of its "direction"? – becko Apr 13 at 18:36
I think the dipole moment is complex is just because it includes the phase between the states. See here. – user6048 Apr 22 at 2:37

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