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电子结构
原子光谱
• 光谱是辐射束的成分显示。当白光通过棱镜时,形成彩虹色
• 连续光谱是由所有波长的可见光组成的光谱,而不连续光谱则是
线光谱代表的原子发射
• 线光谱的产生取决于所使用的元素类型,可见光的发射也取决于
此
分光光度计
• 用于将光分散为单个波长的仪器
• 线光谱的研究可用于:
1. 鉴定元素
2. 确定元素的电离能
3. 确定元素原子中电子的排布
氢的原子发射光谱
在氢原子中,氢的原子发射光谱显示出几个明显的谱线系列。这些
是:
• Lyman系列 – 在紫外区域
• Balmer系列 – 在可见光区域
• Paschen系列 – 在红外区域
下面的图示展示了通过分光光度计产生的线发射示例
原子光谱的形成
• 物质的吸收光谱是通过将物质置于分光光度计中进行检测而产生
的连续辐射光谱
• 因此,在光谱形成过程中存在吸收和发射过程,如下所示:
吸收光谱 发射光谱
• ↑ 当电子占据低能级(基态)时,
吸收光在某一特定频率下被吸收
• ↑ 当足够能量被吸收时,电子能够
“激发”至更高能级
• ↓ 当位于高能级的电子(吸收能量
后)释放能量时,电子回到原来的
基态
• ↓ 当能量释放时,释放辐射,从而
产生光谱,电子以辐射形式释放能
量
光谱特征
• 光谱由离散的谱线组成,每条谱线都具有其自己的离散频率
• 由虚线表示的波长称为光谱(复数形式为spectra)。每个光谱代
表系列中的波长(或频率)。发射的频率可以通过里德堡方程与
光谱线相关联
• 对于氢原子的原子光谱,n1和n2的值如下表所示:
在1900年,马克斯·普朗克提出了量子理论。他提到辐射能以离散
的小包或“量子”形式被发射。每个能量量子 E 与辐射的频率 f 成正
比。
具体而言,能量 E 可以表示为:
E=普朗克常数(h)×频率(f)
• 其中:
普朗克常数 ℎ=6.63×10−34 J sh=6.63×10−34J s
电子能级
• 氢原子的发射光谱由几个系列的不同有限波长的离散线组成。
• 这意味着氢原子不会以所有可能的能量发射光线,而只会以特定能量发射光线
• Bohr提出了这些假设来解释光谱中的线条。电子围绕原子核轨道运动(类似行星绕太阳的
运动):
1. 电子的能量是量子化的(只有一定的能量)
2. 靠近原子核的电子能量较低,反之亦然
3. 原子的电子将首先填满最低能级。但是,当给电子能量时,它会从较低的能级移到较高
的能级。这个过程称为激发
4. 如果从激发的能级到原始能级的能量损失,电子将发射电磁辐射。这就是光谱线的发射
原因。光谱线的收敛显示了随着能级距离原子核的增加,连续能级之间的差异变小
氢的电离能可以通过其线谱来计算
• 当氢光谱的能级增加时,存在一种可能性,即它达到了能级收敛
极限,其中n=∞
• 当这种情况发生时,电子无法返回基态,最终氢原子被电离,根
据以下方程式:
• H(g)→H+(g)+e−
• 要实现这一点,需要一定数量的能量
• 移除一个电子所需的能量称为电离能。在这里,会形成一个带正
电的离子
通过线谱有两种计算氢的电离能的方法
• 使用里德伯格和普朗克方程:
假设处于能级 n1 ​= 1 的电子吸收了能量并被激发。当它
达到收敛极限时,即 n2 ​= ∞,可以计算出波长
使用里德伯格方程 n1​= 1 n2​= ∞
• 对于每个电子,吸收的能量可以通过普朗克方程确定
• 由于激发一个电子需要这么多能量,所以对于1摩尔的电子来说,
所需的能量:
因为1摩尔包含6.02 x 10^23个电子,所以电离能,∆H =
E x N
= 2.182 x 10^-18 J / 个 x 6.02 x 10^23
= 1.313 x 10^6 J / 摩尔
• 因此,氢的电离能是0.1313千焦耳/摩尔
原子轨道
• 海森堡不确定性原理 - 电子的位置和动量不能被准确知道,但可
以计算在某一位置找到电子的概率
• 轨道 - 在其中有很高概率找到电子的空间。轨道中的电子被描述
为占据核周围的三维空间
轨道 - 边界内有95%(高概
率)的机会找到电子
轨道的类型 轨道的形状 填充的电子数
s
2
p 6
d 10
f 7 orbitals 14
填充壳层中的轨道
• 原子壳层中的电子通过占据每个壳层中的轨道来填充
• 用于计算每个壳层可占据轨道数的公式是 :
电子构型
• 一个元素的电子构型是描述该元素内部的电子如何根据其轨道来
填充的表达式
• 有三条规则可以用来确定原子在基态下的轨道的电子分配
1. Aufbau原理
2. Pauli不相容原理
3. Hund规则
Aufbau原理
• 电子按照轨道的能级顺序占据轨道
• 能量最低的轨道始终首先被占据
• 下图显示了能级从最低到最高的排列:
Pauli不相容原理
• 两个电子可能占据同一轨道,但这两个电子的自旋必须相反
Hund规则
• 当电子被放置在具有相同或能量退化的轨道中时,电子必须以平
行自旋的方式单独占据它们,然后再成对占据轨道
• 换句话说,原子倾向于尽可能地拥有尽可能多的未成对电子。例
如:在填充 p 轨道中的 3 个电子时
电子结构.pptx会给机构客户很快就开了、佳偶iujiuojoijiojoikm
电子结构.pptx会给机构客户很快就开了、佳偶iujiuojoijiojoikm
电子结构.pptx会给机构客户很快就开了、佳偶iujiuojoijiojoikm
电子结构.pptx会给机构客户很快就开了、佳偶iujiuojoijiojoikm

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