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Let \\(\\mathcal{L}=-\\Delta+\\mu\\) be the generalized Schr\u00f6dinger operator on \\(\\mathbb{R}^n\\) with \\(n\\geq 3\\), where \\(\\mu\\not\\equiv0\\) is a nonnegative Radon measure satisfying the scale-invariant Kato condition: for all \\(x\\in\\mathbb{R}^n\\) and \\(0<r<R<\\infty\\), NEWLINE\\[NEWLINE\\mu(B(x,r))\\leq C_0(\\frac rR)^{n-2+\\delta}\\mu(B(x,R)),NEWLINE\\]NEWLINE and also the doubling condition: for all \\(x\\in\\mathbb{R}^n\\) and \\(0<r< \\infty\\), NEWLINE\\[NEWLINE\\mu(B(x,2r))\\leq C_1\\{\\mu(B(x,r))+r^{n-2}\\},NEWLINE\\]NEWLINE where \\(C_0,C_1,\\delta\\) are constants independent of \\(x, r\\) and \\(R\\). In this paper, the author prove that the heat kernel \\(\\mathcal{K}_t\\) associated with \\(\\mathcal{L}\\) satisfies the following upper estimate: NEWLINE\\[NEWLINE0\\leq \\mathcal{K}_t(x,y)\\leq Ch_t(x-y)e^{-\\varepsilon d_\\mu(x,y,t)},NEWLINE\\]NEWLINE for some \\(\\varepsilon>0\\), where \\(h_t(x)=(4\\pi t)^{-n/2}e^{-|x|^2/(2t)}\\) and \\(d_\\mu(x,y,t)\\) is some parabolic type distance function with respect to \\(\\mu\\). As applications, a Hardy space with respect to \\(\\mathcal{L}\\) is introduced via maximal functions of heat semigroup \\(e^{-t\\mathcal{L}}\\) and characterized via atoms and Riesz transforms. 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